subject:(Ligands)

1. Tran, Diem Ngan. Nouveaux ligands hétérocycliques et leurs complexes métalliques : étude des propriétés magnétiques : New heterocyclic ligands and their metal complexes : study of their magnetic properties.

Degree: Docteur es, Chimie et Physico-chimie Moléculaire, 2008, Université Henri Poincaré – Nancy I

URL: http://www.theses.fr/2008NAN10076

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Dans le premier temps, nous avons préparé de nouveaux hétérocycles azotés comprenant des unités 1,2,4-triazine : btrz, cpytrz, pytrz, bpy-pytrz et pytrz. Ensuite, nous avons… (more)

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Dans le premier temps, nous avons préparé de nouveaux hétérocycles azotés comprenant des unités 1,2,4-triazine : btrz, cpytrz, pytrz, bpy-pytrz et pytrz. Ensuite, nous avons observé leur aptitude à la complexation des ions métalliques d10 (CuI, AgI, ZnII) en utilisant l’analyse en spectrométrie UV-Visible, spectrométrie de Masse ESIMS, Résonance Magnétique Nucléaire, et Diffraction de Rayons X. En outre, avec le ligand bpy-pytrz, son complexe CuI est un hélicate double-brin dinucléaire dont l’orientation H-H (Head to Head) ou H-T (Head to Tail) sera déterminée grâce à la structure RX. Par ailleurs, nous avons obtenu pour la première fois des monocristaux d’un complexe entre l’ion uranium UO2(NO3)2 et le ligand bpy-pytrz. Dans une seconde partie, la synthèse de séquences bipyridine-bisdiazines-pont 2-oxapropylène est présentée à savoir les séquences : bpy-bpz, bpy-bpm, bpy-btz2,2’ et bpy-btz4,4’. L’étude de leurs modes de complexation avec des ions métalliques 3dn (NiII, CoII, CuII) a été réalisée. Enfin, des résultats intéressants sur les propriétés magnétiques (ferromagnétisme) de ces complexes ont été obtenus et concernent en particulier des complexes neutres dinucléaires du NiII .

Fistly, new nitrogen heterocycles containing 1,2,4-triazine units have been prepared: btrz, cpytrz, pytrz, bpy-pytrz et pytrz. Then, their complexation behaviour have been studied with d10 transition metal ions (CuI, AgI, ZnII) by UV-Vis, Nuclear Magnetic Resonance, ESI-MS and X-ray diffraction spectrometries. Particularly, the bpy-pytrz ligand CuI complex gave a dinuclear double-strand helicate, of which H-H (Head to Head) or H-T (Head to Tail) conformation will be determined by X-ray diffraction. Elsewere, for the first time we were able to obtained suitable single crystals of the Uranium (UO2(NO3)2) complex with bpy-pytrz ligand. Secondly, the synthesis of sequential 2-oxapropylene-bridged bipyridine-bisdiazine strands (bpy-bpz, bpy-bpm, bpy-btz2,2’, bpy-btz4,4’) has been reported. Their complexation behaviour with 3dn transition metal ions (CoII, NiII, CuII) have been studied in solution and in solid phases. Finally, preliminary interesting results have been achieved on the magnetic properties of their complexes and concerned particularly the dinuclear NiII neutral complexes.

Advisors/Committee Members: Marsura, Alain (thesis director), Montaigne, François (thesis director).

Subjects/Keywords: Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Tran, D. N. (2008). Nouveaux ligands hétérocycliques et leurs complexes métalliques : étude des propriétés magnétiques : New heterocyclic ligands and their metal complexes : study of their magnetic properties. (Doctoral Dissertation). Université Henri Poincaré – Nancy I. Retrieved from http://www.theses.fr/2008NAN10076

Chicago Manual of Style (16^th Edition):

Tran, Diem Ngan. “Nouveaux ligands hétérocycliques et leurs complexes métalliques : étude des propriétés magnétiques : New heterocyclic ligands and their metal complexes : study of their magnetic properties.” 2008. Doctoral Dissertation, Université Henri Poincaré – Nancy I. Accessed February 25, 2020. http://www.theses.fr/2008NAN10076.

MLA Handbook (7^th Edition):

Tran, Diem Ngan. “Nouveaux ligands hétérocycliques et leurs complexes métalliques : étude des propriétés magnétiques : New heterocyclic ligands and their metal complexes : study of their magnetic properties.” 2008. Web. 25 Feb 2020.

Vancouver:

Tran DN. Nouveaux ligands hétérocycliques et leurs complexes métalliques : étude des propriétés magnétiques : New heterocyclic ligands and their metal complexes : study of their magnetic properties. [Internet] [Doctoral dissertation]. Université Henri Poincaré – Nancy I; 2008. [cited 2020 Feb 25]. Available from: http://www.theses.fr/2008NAN10076.

Council of Science Editors:

Tran DN. Nouveaux ligands hétérocycliques et leurs complexes métalliques : étude des propriétés magnétiques : New heterocyclic ligands and their metal complexes : study of their magnetic properties. [Doctoral Dissertation]. Université Henri Poincaré – Nancy I; 2008. Available from: http://www.theses.fr/2008NAN10076

Nelson Mandela Metropolitan University

2. Booysen, Irvin Noel. Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group.

Degree: Faculty of Science, 2009, Nelson Mandela Metropolitan University

URL: http://hdl.handle.net/10948/1270

► The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V)… (more)

▼ The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab = 1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only in a distorted octahedral coordination geometry around the metal ion. The complex trans- [Re(ada)Cl3(PPh3)2] (H2ada = 2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The ‘2 + 1’ complex fac- [Re(CO)3(Hamp)(amp)] (Hamp = 2-aminophenol) was isolated from the reaction of a two molar ratio of Hamp with [Re(CO)5Br] in toluene. The reaction of a 1:1 molar ratio of [Re(CO)5Br] and H2ada led to the isolation of the Re(I) complex, fac- [Re(CO)3Br(H2ada)]. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of trans-[ReOCl3(PPh3)2] with N-(2-aminobenzylidene)-5-amino-1,3-dimethyl uracil (H3dua) in ethanol gave a mixed crystal which contains both the neutral oxorhenium(V) complex [ReOCl(Hdua)] and the imido rhenium(V) [Re(dua)Cl2(PPh3)] in an equimolar ratio in the asymmetric unit. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux led to the isolation of [C12H12N6O4] as only product. The [ReO4]- anion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination Abstract I.N. Booysen Nelson Mandela Metropolitan University vii of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of 2-(2-aminophenyl)benzothiazole (Habt) with [Re(CO)5Br] led to the isolation of the rhenium(I) complex fac-[Re(Habt)(CO)3Br]. With trans-[ReOCl3(PPh3)2], the ligand Habt decomposed to form the oxofree rhenium(V) complex [Re(itp)2Cl(PPh3)] (itp = 2-amidophenylthiolate). From the reaction of trans-[ReOBr3(PPh3)2] with 2-(2- hydroxyphenyl)benzothiazole (Hhpd) the complex [ReVOBr2(hpd)(PPh3)] was obtained. The reaction of a twofold molar excess of H2apb (2-(2-aminophenyl)-1-benzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonalbipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each…

Subjects/Keywords: Rhenium; Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Booysen, I. N. (2009). Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group. (Thesis). Nelson Mandela Metropolitan University. Retrieved from http://hdl.handle.net/10948/1270

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Booysen, Irvin Noel. “Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group.” 2009. Thesis, Nelson Mandela Metropolitan University. Accessed February 25, 2020. http://hdl.handle.net/10948/1270.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Booysen, Irvin Noel. “Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group.” 2009. Web. 25 Feb 2020.

Vancouver:

Booysen IN. Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group. [Internet] [Thesis]. Nelson Mandela Metropolitan University; 2009. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10948/1270.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Booysen IN. Rhenium (I) and (V) complexes with potentially mulidentate ligands containing the Amino group. [Thesis]. Nelson Mandela Metropolitan University; 2009. Available from: http://hdl.handle.net/10948/1270

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Tasmania

3. Batten, Michael Peter. Imidazole substituted ligands in late transitional metal catalysis : comparative synthetic, spectroscopic and catalytic studies.

Degree: 2008, University of Tasmania

URL: https://eprints.utas.edu.au/19252/1/whole_BattenMichaelPeter2008_thesis.pdf

► This thesis addresses the chemistry of imidazole containing ligands, particularly with respect to their nickel, iron and molybdenum complexes. The ability of many of the… (more)

Subjects/Keywords: Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Batten, M. P. (2008). Imidazole substituted ligands in late transitional metal catalysis : comparative synthetic, spectroscopic and catalytic studies. (Thesis). University of Tasmania. Retrieved from https://eprints.utas.edu.au/19252/1/whole_BattenMichaelPeter2008_thesis.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Batten, Michael Peter. “Imidazole substituted ligands in late transitional metal catalysis : comparative synthetic, spectroscopic and catalytic studies.” 2008. Thesis, University of Tasmania. Accessed February 25, 2020. https://eprints.utas.edu.au/19252/1/whole_BattenMichaelPeter2008_thesis.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Batten, Michael Peter. “Imidazole substituted ligands in late transitional metal catalysis : comparative synthetic, spectroscopic and catalytic studies.” 2008. Web. 25 Feb 2020.

Vancouver:

Batten MP. Imidazole substituted ligands in late transitional metal catalysis : comparative synthetic, spectroscopic and catalytic studies. [Internet] [Thesis]. University of Tasmania; 2008. [cited 2020 Feb 25]. Available from: https://eprints.utas.edu.au/19252/1/whole_BattenMichaelPeter2008_thesis.pdf.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Batten MP. Imidazole substituted ligands in late transitional metal catalysis : comparative synthetic, spectroscopic and catalytic studies. [Thesis]. University of Tasmania; 2008. Available from: https://eprints.utas.edu.au/19252/1/whole_BattenMichaelPeter2008_thesis.pdf

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Nelson Mandela Metropolitan University

4. Abrahams, Abubak'r. The coordination chemistry of Rhenium(V) with multidentate no-donor ligands.

Degree: PhD, Faculty of Science, 2009, Nelson Mandela Metropolitan University

URL: http://hdl.handle.net/10948/912

► The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a… (more)

▼ The neutral distorted octahedral complexes [ReOCl(L)] {H2L = N,N-bis(2- hydroxybenzyl)-2-(2-aminoethyl)dimethylamine (H2had), N,N-bis(2-hydroxybenzyl) aminomethylpyridine (H2hap); N,N-bis(2-hydroxybenzyl)-2-(2-aminoethyl)pyridine (H2hae)} were prepared by the reaction of trans-[ReOCl3(PPh3)2] with a twofold molar excess of H2L in ethanol. The X-ray structure determinations of [ReOCl(had)] and [ReOCl(hap)] were performed, and in both complexes the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen. Treatment of trans-[ReO2(py)4]I with two equivalents and one equivalent each of H2had in acetone afforded the iodide salts of the oxypyridinium-ammonium zwitterions N1-(2-hydroxybenzyl)-N2,N2- dimethyl-N1-((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [Hhpd]+ and N2,N2- dimethyl-N1-bis((2-oxypyridinium)-1-methyl)ethane-1,2-diamine [dod]+ respectively. In [Hhpd]I, one of the 2-hydroxyphenyl groups of H2had is substituted by an oxypyridinium group, and in [dod]I, both 2-hydroxyphenyl groups are converted. The X-ray crystal structure determination of the starting material H2had, [Hhpd]I and [dod]I reveals trigonal pyramidal geometries around the central amino nitrogen. The complex salt [ReO(bsa)]PF6 (H2bsa=bis(N-methylsalicylicylideneiminopropyl) amine) was prepared from the reaction of cis-[ReO2I(PPh3)2] with H2bsa in toluene. The dianionic pentadentate ligand bsa is coordinated to the ReO3+ moiety via one secondary amino and two imino nitrogens, and two anionic phenolate oxygens. The complex was characterized by spectroscopy and analytical data, and the structure has been determined by single-crystal X-ray diffraction analysis. The complex exhibits a distorted octahedral geometry around the central rhenium(V) ion, with the basal plane being defined by a phenolate oxygen, two imino nitrogens and the secondary amino. ix A. Abrahams Nelson Mandela Metropolitan University The reaction of a two-fold molar excess of the potentially NN-donor ligand 2,2’- dipyridylamine (dpa) with trans-[ReO(OEt)Cl2(PPh3)2] in ethanol led to the isolation of [ReOCl2(OEt)(dpa)]. The X-ray crystal structure shows that the NN-chelated dpa is coordinated in the equatorial plane cis to the oxo and ethoxo groups, which are in trans positions relative to each other. The treatment of trans- [ReOCl3(PPh3)2] with a tenfold molar excess of dpa in ethanol at the refluxing temperature yielded the trans-dioxo complex [ReO2(dpa)2]Cl, but with a twofold molar excess only (μ-O)[{ReOCl2(dpa)}2] was isolated. Repeating the latter reaction with (n-Bu4N)[ReOCl4] as starting material in ethanol at room temperature a dark green product, also with the formulation (μ-O)[{ReOCl2(dpa)}2], was isolated. The reaction of equimolar quantities of bis(pyridin-2-yl)methyl)amine (HBPA) with (n-Bu4N)[ReOCl4] in acetone at room temperature led to the isolation of the sixcoordinate rhenium(V) complex [ReOCl(H2O)(BPA)]Cl. IR, NMR and X-ray crystallographic results indicate that BPA is coordinated as a tridentate… Advisors/Committee Members: Gerber, T I A Prof.

Subjects/Keywords: Rhenium; Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Abrahams, A. (2009). The coordination chemistry of Rhenium(V) with multidentate no-donor ligands. (Doctoral Dissertation). Nelson Mandela Metropolitan University. Retrieved from http://hdl.handle.net/10948/912

Chicago Manual of Style (16^th Edition):

Abrahams, Abubak'r. “The coordination chemistry of Rhenium(V) with multidentate no-donor ligands.” 2009. Doctoral Dissertation, Nelson Mandela Metropolitan University. Accessed February 25, 2020. http://hdl.handle.net/10948/912.

MLA Handbook (7^th Edition):

Abrahams, Abubak'r. “The coordination chemistry of Rhenium(V) with multidentate no-donor ligands.” 2009. Web. 25 Feb 2020.

Vancouver:

Abrahams A. The coordination chemistry of Rhenium(V) with multidentate no-donor ligands. [Internet] [Doctoral dissertation]. Nelson Mandela Metropolitan University; 2009. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10948/912.

Council of Science Editors:

Abrahams A. The coordination chemistry of Rhenium(V) with multidentate no-donor ligands. [Doctoral Dissertation]. Nelson Mandela Metropolitan University; 2009. Available from: http://hdl.handle.net/10948/912

Nelson Mandela Metropolitan University

5. Booysen, Irvin Noel. Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group.

Degree: MSc, Faculty of Science, 2007, Nelson Mandela Metropolitan University

URL: http://hdl.handle.net/10948/479

► The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through… (more)

▼ The complex trans-[Re(dab)Cl3(PPh3)2] (H2dab=1,2-diaminobenzene) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2dab in ethanol. The ligand dab is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. The complex trans-[Re(ada)Cl3(PPh3)2] (H2ada=2-aminodiphenylamine) was prepared from the reaction of trans-[ReOCl3(PPh3)2] with H2ada in acetonitrile. The ligand ada is coordinated to the rhenium(V) centre through a dianionic imido nitrogen only, in a distorted octahedral coordination geometry around the metal ion. Surprisingly, the Re-Cl bond length trans to the Re=N bond is shorter than the two equatorial Re-Cl bond lengths. The reaction of equimolar quantities of cis-[ReO2I(PPh3)2] with 5,6-diamino-1,3- dimethyluracil (H2ddd) in acetonitrile led to the formation of [Re(ddd)(Hddd)I(PPh3)2](ReO4). The X-ray crystal structure shows that the ligand ddd is coordinated monodentately through the doubly deprotonated amino nitrogen and is therefore present as an imide. The chelate Hddd is coordinated bidentately via the neutral amino nitrogen, which is coordinated trans to the imido nitrogen, and the singly deprotonated amido nitrogen, trans to the iodide. The reaction of equimolar quantities of [NH4(ReO4)] with H2ddd in methanol under reflux conditions led to the isolation of [C12H12N6O4] as only product. The [ReO4]- ion is therefore instrumental in the formation of [C12H12N6O4], and since the product contains no rhenium in any oxidation state, the conclusion is that [ReO4]- catalyses the oxidative deamination of H2ddd. The X-ray crystal structure consists of two centrosymmetric, tricyclic rings, comprising a central pyrazine ring and two terminal pyrimidine rings. The reaction of a twofold molar excess of H2apb (H2apb=2-(2-aminophenyl)-1Hbenzimidazole) with trans-[ReO2(py)4]Cl in ethanol gave the green product of the formulation [ReO(Hapb)(apb)] in good yield. The rhenium atom lies in a distorted trigonal-bipyramidal environment. The two imidazole N(2) atoms lie in the apical positions trans to each other, with the oxo-oxygen and two amido N(1) atoms in the trigonal plane. The complex has C2-symmetry. The two amino groups are singly deprotonated and provide a negative charge each, so that they are coordinated as amides. The oxo group provides two negative charges. In order to obtain electroneutrality for the rhenium(V) complex, the two coordinated imidazole nitrogens provide one negative charge. The complex salt trans-[Re(mps)Cl(PPh3)2](ReO4) (H3mps=N-(2-amino-3- methylphenyl)salicylideneimine) was prepared by the reaction of trans- [ReOCl3(PPh3)2] with a twofold molar excess of H3mps. The X-ray crystal structure shows that the trianionic ligand mps acts as a tridentate chelate via the doubly deprotonated amino nitrogen (which is present in trans- [Re(mps)Cl(PPh3)2](ReO4) as an imide), the neutral imino nitrogen and the deprotonated phenolic oxygen. The [ReO4]- anion has approximately regular tetrahedral geometry.… Advisors/Committee Members: Gerber, T I A Prof, Tshentu, Z R Dr.

Subjects/Keywords: Rhenium; Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Booysen, I. N. (2007). Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group. (Masters Thesis). Nelson Mandela Metropolitan University. Retrieved from http://hdl.handle.net/10948/479

Chicago Manual of Style (16^th Edition):

Booysen, Irvin Noel. “Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group.” 2007. Masters Thesis, Nelson Mandela Metropolitan University. Accessed February 25, 2020. http://hdl.handle.net/10948/479.

MLA Handbook (7^th Edition):

Booysen, Irvin Noel. “Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group.” 2007. Web. 25 Feb 2020.

Vancouver:

Booysen IN. Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group. [Internet] [Masters thesis]. Nelson Mandela Metropolitan University; 2007. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10948/479.

Council of Science Editors:

Booysen IN. Rhenium(V)-Imido complexes with potentially multidentate ligands containing the amino group. [Masters Thesis]. Nelson Mandela Metropolitan University; 2007. Available from: http://hdl.handle.net/10948/479

6. Pinder, Tiffany. Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals.

Degree: 2013, Texas Digital Library

URL: http://hdl.handle.net/1969; http://hdl.handle.net/2249.1/66797

► Metallodithiolate ligands play an important role in providing the appropriate electronic environment for the catalytic function of various metalloenzymes; acetyl coA synthase serves as paradigm.… (more)

▼ Metallodithiolate ligands play an important role in providing the appropriate electronic environment for the catalytic function of various metalloenzymes; acetyl coA synthase serves as paradigm. Using tetradentate N_(2)S_(2) ligands to bind transition metals, a library of well-characterized synthetic analogues has been established. These metal-bound cis-dithiolates, display a wide range of reactivity, including S-based metallation, oxygenation, and alkylation. Sulfur???s affinity for gold(I) is well known and typically follows Pearson???s HSAB theory. With this in mind, the NiN_(2)S_(2) moieties were used to synthesize propeller-type nickel-gold complexes within a group of [Ni(N_(2)S_(2))_(x)Au_(y)] ( x = 1 or 2; y = 1, 2, or 4) complexes. The solid-state molecular structures of these square planar cis-dithiolate nickel complexes to which gold(I) is bound contain within them classical aurophilic interactions. Electrochemical studies reveal a positive shift in the Ni^(II/I) couple for the [Ni(N_(2)S_(2))_(x)Au_(y)] complexes as compared to the NiN_(2)S_(2) precursors. The incorporation of the paramagnetic vanadyl ion, [V???O]^(2+), in N_(2)S_(2) motifs has been studied in our laboratory. Previous studies of M(N_(2)S_(2)) complexes where M is Ni^(2+), ZnCl^(+), and Fe(NO) with the W(CO)_(x) reporter unit have been explored to determine the donor ability of these metallodithiolate ligands. According to their response or binding to a tungsten carbonyl unit, we have found that the sulfurs of the dianionic [(V???O)(ema)]^(2-) are activated as nuclephilies. To further investigate the donor ability of the neutral vanadyl-bound thiolate sulfurs, the oxidized {Fe(NO)_(2)}^(9) unit was used. Cleavage of the (??-I)_(2)[Fe(NO)_(2)]_(2) dimer (in the {Fe(NO)_(2)}^(9) form) was achieved with two metalloligands, Ni(bme-daco) and (V???O)bme-daco, and also N-heterocyclic carbene, IMes. Using infrared spectroscopy, the ??(NO) stretching frequencies of the LFe(NO)_(2)I (L = Ni(bme-daco), (V???O)bme-daco, and IMes) complexes were used to report the donor ability of the ligands. Cyclic voltammetry for the LFe(NO)_(2)I complexes show a more accessible {Fe(NO)_(2)}^(9/10) couple for stronger donors. Electron paramagnetic resonance (EPR) measurements of the LFe(NO)_(2)I complexes demonstrate super-hyperfine coupling of the ^(127)I to the unpaired electron on iron, and complex equilibria that indicates dissociation of the metallodithiolate ligand from the dinitrosyl iron unit. Advisors/Committee Members: Darensbourg, Marcetta Y (advisor).

Subjects/Keywords: Metallodithiolate ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Pinder, T. (2013). Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals. (Thesis). Texas Digital Library. Retrieved from http://hdl.handle.net/1969; http://hdl.handle.net/2249.1/66797

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Pinder, Tiffany. “Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals.” 2013. Thesis, Texas Digital Library. Accessed February 25, 2020. http://hdl.handle.net/1969; http://hdl.handle.net/2249.1/66797.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Pinder, Tiffany. “Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals.” 2013. Web. 25 Feb 2020.

Vancouver:

Pinder T. Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals. [Internet] [Thesis]. Texas Digital Library; 2013. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/1969; http://hdl.handle.net/2249.1/66797.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Pinder T. Development of Metallodithiolates as a New Class of Versatile Ligands to Transition Metals. [Thesis]. Texas Digital Library; 2013. Available from: http://hdl.handle.net/1969; http://hdl.handle.net/2249.1/66797

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Nelson Mandela Metropolitan University

7. Habarurema, Gratien. Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands.

Degree: MSc, Faculty of Science, 2013, Nelson Mandela Metropolitan University

URL: http://hdl.handle.net/10948/d1020952

► This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the… (more)

▼ This study investigates the coordination modes of potential multidentate N,O-donor Schiff base ligands to the [ReVO]3+ and fac-[ReI(CO)3]+ cores. The project is aimed at the synthesis of tridentate, tetradentate and pentadentate Schiff bases ligands derived from the condensation reactions of benzaldehyde with different primary amines. The structures of these Schiff bases and their complexes were confirmed by using physical characterization methods, namely melting points, UV-Visible, UV-emission, 1H NMR and IR spectroscopy, X-ray diffractometry and elemental analysis. To further understand the coordination chemistry of rhenium, the prepared diiminediphenol N2O2-donor Schiff base ligand N N′-o-phenylene-bis(salicylaldimine) (H2salphen) was reacted with trans-[ReOCl3(PPh3)2] to yield cis-[ReCl2(ophsal)(PPh3)], whereas its reaction with trans-[ReOBr3(PPh3)2] resulted in the formation of the cis-[ReBr2(aphsal)(PPh3)].2CH3CN complex. In the above complexes the H2salphen ligand was cleaved leading to the coordinated tridentate ophsal NO2- and aphsal N2O-donor ligands. The reaction of H3aphsal with trans-[ReOBr3(PPh3)2] in toluene led to an unexpected compound, trans- [{[ReBr(aphsal)(PPh3)2]Br}{[ReBr(aphsal)(PPh3)2](ReO4)}] with an imido [ReNR]3+core. The ligand aphsal was coordinated tridentately with the doubly deprotonated amino nitrogen leading to Re(V)-imido complexes. The reaction of 2-((Z)-(2-aminoethylimino)methyl)phenol (H3amphol) with [Re(CO)5Cl] led to the rhenium(I) product fac-[Re(CO)3(H3amphol)] with H3amphol coordinated as a monoanionic tridentate chelate through its phenolate oxygen and amino nitrogen atoms. The X-ray crystal structures showed that all complexes display a distorted octahedral geometry around the central rhenium atom. The reaction of 2,6-bis(2-hydroxyphenylimino)pyridine (H2hpp) with cis-[ReO2I(PPh3)2] resulted in the reduced Re(III) product trans-[Re(hpp)(PPh3)2]I, while trans-[Re(hpp)(PPh3)2](ReO4) was isolated from its reaction with trans-[ReOCl3(PPh3)2]. The H2hpp ligand acts as a pentadentate N3O2-donor ligand where the two phenolic protons undergo deprotonation and its three nitrogens act as neutral donor atoms. Both compounds resulted from a disproportionation reaction characterized by the produced perrhenate counter-ion. The complex fac-[Re(CO)3(H2hpp)Cl] was prepared from [Re(CO)5Cl] and H2hpp in toluene. The H2hpp ligand acted as a neutral bidentate N,N-donor chelate. The metal is coordinated to three carbonyl donors in a facial orientation, two neutral nitrogen atoms and a chloride ligand. The reactions of the potentially tetradentate ligand N,N'-ethylenebis(salicylideneimine) (H2salen) with different rhenium(V) precursors resulted in the formation of two dimeric oxorhenium (V) compounds. In the reaction of H2salen with trans-[ReOCl3(PPh3)2] in ethanol, the highly unusual distorted dimeric complex (μ-salen)[ReOCl2(PPh3)]2 was isolated, in which salen2- is coordinated as a tetradentate to two oxorhenium(V) centres, and salen2- is present as a bidentate monoanionic ligand on each… Advisors/Committee Members: Gerber, T I A Prof.

Subjects/Keywords: Rhenium; Ligands

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APA (6^th Edition):

Habarurema, G. (2013). Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands. (Masters Thesis). Nelson Mandela Metropolitan University. Retrieved from http://hdl.handle.net/10948/d1020952

Chicago Manual of Style (16^th Edition):

Habarurema, Gratien. “Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands.” 2013. Masters Thesis, Nelson Mandela Metropolitan University. Accessed February 25, 2020. http://hdl.handle.net/10948/d1020952.

MLA Handbook (7^th Edition):

Habarurema, Gratien. “Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands.” 2013. Web. 25 Feb 2020.

Vancouver:

Habarurema G. Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands. [Internet] [Masters thesis]. Nelson Mandela Metropolitan University; 2013. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10948/d1020952.

Council of Science Editors:

Habarurema G. Rhenium (I), (III) and (V) complexes with potentially multidentate N, O-Donor ligands. [Masters Thesis]. Nelson Mandela Metropolitan University; 2013. Available from: http://hdl.handle.net/10948/d1020952

Nelson Mandela Metropolitan University

8. Yumata, Nonzaliseko Christine. Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands.

Degree: Faculty of Science, 2010, Nelson Mandela Metropolitan University

URL: http://hdl.handle.net/10948/1085

► The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep… (more)

▼ The reaction of the potentially tridentate Schiff-base chelate Hhaep [Haep = N’-(1- (2-hydroxyphenyl)ethylidene)benzohydrazide] with [ReCl3(benzil)(PPh3)] and trans-[ReOCl3(PPh3)2] produced the neutral oxorhenium(V) complexes cis- [ReOCl2(mep)] [Hmep = 2-(1-iminoethyl)phenol] and cis-[ReOCI2(meb)(PPh3)] [Hmeb = N’-(propan-2-ylidene)benzohydrazide] in ethanol and acetone respectively. In both reactions the Hhaep molecule cleaves to give different coordinated bidentate NO-donor chelates coordinated to the rhenium(V) centers. The X-ray studies reveal that mep is present as a bidentate, monoanionic Schiffbase coordinating through the neutral imino nitrogen and the deprotonated phenolate oxygen in cis-[ReOCl2(mep)]. The bond distances and angles in cis- [ReOCI2(meb)(PPh3)] confirm that meb coordinates to the metal in the enolate form. The distorted octahedral complex fac-[ReCl3(dpa)(PPh3)] was prepared by the reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of dpa in acetonitrile under a nitrogen atmosphere. The compound dpa.HCl.2H2O was obtained as a by-product in the reaction of dpa with trans-[ReCI3(MeCN)(PPh3)2] in acetonitrile. The reaction of trans-[ReCl3(MeCN)(PPh3)2] with a twofold molar excess of 6- amino-3-methyl-1-phenyl-4-azahept-2-ene-1-one (Hamp) in acetonitrile led to the isolation of cis-[ReCl2(bat)(PPh3)2]. On complexation to the metal center Hamp decomposed to give the coordinated benzoylacetone (bat). Bat is present as a monoanionic bidentate chelate. The complexes [ReVOCI(had)] and [ReIVCl(had)(PPh3)](ReO4) were prepared from the reaction of trans-[ReCl3(MeCN)(PPh3)2] with N,N-bis((2-hydroxybenzyl)-2- aminoethyl)dimethylamine (H2had) in ethanol under various reaction conditions. The treatment of [ReCl3(benzil)(PPh3)] with 2-[((2- pyridinylmethyl)amino)methyl]phenol (Hham) in a 2:1 molar ratio in acetonitrile led to the isolation of the hydrogen-bonded dimer [ReOCl2(ham)]2. The distorted octahedral complex [ReOCl(hap)] [H2hap = N,N-bis(2- hydroxybenzyl)aminomethylpyridine] was prepared from the reaction of trans- [ReCl3(MeCN)(PPh3)2] with a twofold molar excess of H2hap in acetonitrile. The X-ray crystal structure analysis shows that the chloride is coordinated trans to the tripodal tertiary amino nitrogen, with a phenolate oxygen trans to the oxo oxygen.

Subjects/Keywords: Rhenium; Ligands

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APA (6^th Edition):

Yumata, N. C. (2010). Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands. (Thesis). Nelson Mandela Metropolitan University. Retrieved from http://hdl.handle.net/10948/1085

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Yumata, Nonzaliseko Christine. “Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands.” 2010. Thesis, Nelson Mandela Metropolitan University. Accessed February 25, 2020. http://hdl.handle.net/10948/1085.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Yumata, Nonzaliseko Christine. “Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands.” 2010. Web. 25 Feb 2020.

Vancouver:

Yumata NC. Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands. [Internet] [Thesis]. Nelson Mandela Metropolitan University; 2010. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10948/1085.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Yumata NC. Reactivity of Rhenium (iii) and Rhenium (V) with multidentate NN-and no-donor ligands. [Thesis]. Nelson Mandela Metropolitan University; 2010. Available from: http://hdl.handle.net/10948/1085

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Massey University

9. Ingham, Scott Law. Structural studies on complexes with multidentate ligands.

Degree: PhD, Chemistry, 1991, Massey University

URL: http://hdl.handle.net/10179/12961

► The results reported in this thesis are an investigation into the coordination abilities of some multidentate ligands, the majority of which possess more than one… (more)

▼ The results reported in this thesis are an investigation into the coordination abilities of some multidentate ligands, the majority of which possess more than one type of donor atom. In Section One studies on the reactivity of triosmium cluster compounds with phenylthioureas and substituted triphenylphosphines are reported. Section Two details the results of studies on selected multidentate ligands containing phosphorus and nitrogen donor atoms. Section One Chapter 1 is a brief overview of osmium cluster compounds reported to date in the literature and in particular the reactions of triosmium clusters with organic substrates, organosulphur compounds and phosphines. In Chapter 2 the reactions of the 'lightly stabilised' triosmium cluster [Os3(CO)i 0(CH3CN)2] with phenylthiourea and diphenylthiourea are reported. Single crystal X-ray structural determinations were performed for the compounds [HOs3(CO) x(dptu)] (where x = 9, 10 dptu = diphenylthiourea). The photochemically induced decarbonylation of the clusters [HOs3(CO)io(L)] ( where L = phenylthiourea, diphenylthiourea) has also been investigated, with quantum yields and apparent activation energies reported. Detailed in Chapter 3 are the results of studies on the reactivity of triphenylphosphine ligands which possess aldehyde (2-PCHO, 4-PCHO) or amine (2-PNH2, 3-PNH2) substituents, with the triosmium clusters [Os3(C0)12-x(CH3CN)xJ (where x = 1, 2). A single crystal X-ray structural determination was performed on the complex [HOs3(C0)9(2-PNH)]. Section Two Chapter 4 is a brief overview of the use of multidentate ligands in forming coordination complexes with transition metals. The results of an investigation on the coordination complexes of Cu(l) and Ag(I) with the potentially tridentate ligands pyridine-2-carbaldehyde 2'-pyridylhydrazone and 2,2':6',2"-terpyridine are reported in Chapter 5. Many of these compounds have been shown by single crystal X-ray structural determinations to possess an unusual five coordinate stereochemistry at the metal centre. In Chapter 6 the results of studies on the coordination complexes of Cu(I) and Ni(II) with mixed phosphorus and nitrogen donor ligands are reported. These have been shown to form stable complexes where both the phosphorus and nitrogen donor atoms are coordinated.

Subjects/Keywords: Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Ingham, S. L. (1991). Structural studies on complexes with multidentate ligands. (Doctoral Dissertation). Massey University. Retrieved from http://hdl.handle.net/10179/12961

Chicago Manual of Style (16^th Edition):

Ingham, Scott Law. “Structural studies on complexes with multidentate ligands.” 1991. Doctoral Dissertation, Massey University. Accessed February 25, 2020. http://hdl.handle.net/10179/12961.

MLA Handbook (7^th Edition):

Ingham, Scott Law. “Structural studies on complexes with multidentate ligands.” 1991. Web. 25 Feb 2020.

Vancouver:

Ingham SL. Structural studies on complexes with multidentate ligands. [Internet] [Doctoral dissertation]. Massey University; 1991. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10179/12961.

Council of Science Editors:

Ingham SL. Structural studies on complexes with multidentate ligands. [Doctoral Dissertation]. Massey University; 1991. Available from: http://hdl.handle.net/10179/12961

Massey University

10. Ranford, John David. Physicochemical and structural studies on two tridentate antitumour ligand systems.

Degree: PhD, chemistry, 1988, Massey University

URL: http://hdl.handle.net/10179/4193

► This work is an investigation into the physicochemical and structural properties of two tridentate, antitumour ligand systems and is divided into two sections. In the… (more)

▼ This work is an investigation into the physicochemical and structural properties of two tridentate, antitumour ligand systems and is divided into two sections. In the first (Chapters 1 to 4), the ligand 2-formylpyridine thiosemicarbazone (LH - containing an NNS donor set), several of its congeners and a range of complexes (predominantly Cu(II)) were prepared. The second section (Chapters 5 and 6) deals with a range of ligands based on salicylaldehyde benzoylhydrazone (sbH2 - containing an ONO donor set), their complexes (predominantly Cu(II)) and the cytotoxicity data for all of this work. In Chapter 1 , complexes of the general formulation [CuLX]2 for the deprotonated and [Cu (LH)XhX2 for the neutral, protonated ligand were prepared (where X = e.g. halide, pseudohalide, NOj, Cl04, CH3COO-, CF3COO-). The complexes formed are very stable in strong, non-oxidising acid solutions and with roildly reducing anions, but are susceptible to oxidising acids and anions. The crystal structures of the neutral ligand, dimeric, one-atom anion bridged complex [Cu(LH)(CF3C00)]2(CF3C00)2 and the monomeric complex [Cu(LH)(Cl04hH20}2H20 with axially coordinated perchlorato groups were determined. In Chapter 2, the possibility that in vivo S and N donor atom adducts of CuL + may form was investigated in vitro. Stable complexes containing a copper(II)-thiolato bond were isolated at ambient temperatures, under aerobic conditions. The e.s.r. parameters for these were very similar to a species formed from the interaction of CuL + with human blood components. Ternary, Lewis-base adducts of nitrogen donor atoms were also isolated, and the crystal structures for two of these, [CuL(2,2'-bipyridyl)]Cl04 and [CuL(saccharinato)H20J·Y2H20, were solved. The possibility of CuL + interacting with 0 donor groups (in particular phosphates) in vivo was investigated in vitro in Chapter 3. The ternary complexes isolated contain the anions monoiv and dihydrogenphosphate, pyrophosphate, phenolate and molybdate. The crystal structure of [Cu(LH)(H2P04)h(H2P04)2(H3P04h·2H20 showed the complex is dimeric, having a unique one-atom dihydrogenphosphate bridge, three inequivalent phosphates and a very strong interphosphate hydrogen-bond. In contrast, the ternary, pyrophosphate complex [(CuL)4P207} l2H20 is a tetramer, with each Cu(II) centre having a one-atom S, a three-atom pyrophosphate and two five-atom pyrophosphate bridges. The low temperature magnetic properties of [CuL(CH3 C00)]2 fit the Bleany-Bowers expression well, whereas for [(CuL)4P207} l2H20 a very weak interaction through the fiveatom pyrophosphate bridge may account for the non-dimeric behaviour observed. Both complexes are weakly antiferromagnetic (-2J -6 cm-1). In Chapter 4, four variations on the ligand LH and a representative series of their Cu(II) complexes were synthesised. Reduction potentials for a Cu(II) complex of each ligand, as well as for two thiolato and a Lewis-base adduct of CuL +, were measured. N.m.r. spectroscopy was used to characterise the…

Subjects/Keywords: Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Ranford, J. D. (1988). Physicochemical and structural studies on two tridentate antitumour ligand systems. (Doctoral Dissertation). Massey University. Retrieved from http://hdl.handle.net/10179/4193

Chicago Manual of Style (16^th Edition):

Ranford, John David. “Physicochemical and structural studies on two tridentate antitumour ligand systems.” 1988. Doctoral Dissertation, Massey University. Accessed February 25, 2020. http://hdl.handle.net/10179/4193.

MLA Handbook (7^th Edition):

Ranford, John David. “Physicochemical and structural studies on two tridentate antitumour ligand systems.” 1988. Web. 25 Feb 2020.

Vancouver:

Ranford JD. Physicochemical and structural studies on two tridentate antitumour ligand systems. [Internet] [Doctoral dissertation]. Massey University; 1988. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10179/4193.

Council of Science Editors:

Ranford JD. Physicochemical and structural studies on two tridentate antitumour ligand systems. [Doctoral Dissertation]. Massey University; 1988. Available from: http://hdl.handle.net/10179/4193

University of British Columbia

11. MacNeil, Patricia Ann. Hybrid multidentate ligands : amido phosphine complexes of the Group VIII metals .

Degree: 1983, University of British Columbia

URL: http://hdl.handle.net/2429/24322

► The hybrid ligands HN(SiMe₂CH₂PPh₂)₂ and HN(CgH₅CH₂)(SiMe₂CH₂PPh₂) react readily with n-butyl lithium to yield the corresponding lithium salts. Metathesis of Group VIII transition metal halides with… (more)

▼ The hybrid ligands HN(SiMe₂CH₂PPh₂)₂ and HN(CgH₅CH₂)(SiMe₂CH₂PPh₂) react readily with n-butyl lithium to yield the corresponding lithium salts. Metathesis of Group VIII transition metal halides with LiN(SiMe₂CH₂PPh₂)₂ produces a variety of amido phosphine complexes. For the nickel triad, these derivatives have the formula [MCIN(SiMe₂CH₂PPh₂)₂] (M = Ni, Pd, Pt); a variety of rhodium and iridium complexes [M(L)N(SiMe₂CH₂PPh₂)₂] (M = Rh, Ir; L = CO, n²-C₈H₁₄,C₂H₄,PMe₃,PPh₃) and [M(C0D)N(CgH₅CH₂)(SiMe₂CH₂PPh₂)] (M = Rh, Ir; COD = 1,5-cyclooctadiene) have also been prepared and characterized. Single crystal x-ray structural analysis of [NiClN(SiMe₂CH₂PPh₂)₂] indicates that it adopts a distorted square planar stereochemistry, whereas the palladium analogue [PdClN(SiMe₂CH₂PPh₂)₂] is almost perfectly square planar. Based primarily on spectral data, all of these Group VIII amido phosphines are assigned square planar geometries with mutually trans phosphines, with the tridentate ligand coordinated to the metal through the amide nitrogen and both phosphine centres. The amino phosphine dichlorides, [MCI₂NH(SiMe₂CH₂PPh₂)₂] (M = Ni, Pd, Pt) are prepared from the free ligand. The nickel derivative, [NiCl₂NH(SiMe₂CH₂PPh₂)₂], has been shown by crystallographic analysis to have a very distorted tetrahedral geometry; no interaction between the NH moiety and the nickel centre is observed. Reaction of these amino phosphines with triethyl amine cleanly produces the corresponding amido phosphines. [NiClN(SiMe₂CH₂PPh₂)₂] reacts at low temperatures with Grignards or alkyl lithium reagents to yield a series of hydrocarbyl complexes [Ni(R)N(SiMe₂CH₂PPh₂)₂] (R = Me, allyl, vinyl, phenyl). These alkyl (aryl) complexes react readily at room temperature under one atmosphere of carbon monoxide to give Ni(0) species, [Ni(C0)₂N(C0R)(SiMe₂CH₂PPh₂)₂], in which the ligand chelates in a bidentate fashion (through the phosphines) owing to migration of the acyl group to the amide nitrogen. For the methyl and phenyl derivatives, the intermediate Ni(II) acyl complexes have also been isolated. As shown by crystal structural analysis, insertion of CO into the nickel vinyl bond results in an n²-acryloyl Ni(0) species in which the hybrid ligand has undergone further rearrangement to an imidate structure. Some of the rhodium and iridium amidophosphines, lM(L)N(SiMe₂CH₂PPh₂)₂] (M = Rh, L = n²-C₈H₁₄,PPh₃; M = Ir, L = n²-C₈H₁₄, C₂H₄) and [M(COD)N(C₆H₅CH₂) (SiMe₂CH₂PPh₂)] (M = Rh.Ir) are catalyst precursors for the homogeneous hydrogenation of simple olefins under mild conditions (1 atm. H2, 22°C). For the rhodium amido phosphines, olefin isomerization is a competing process with hydrogenation, whereas with [lr(n –C₈H₄)N(SiMe₂CH₂PPh₂)₂] only straightforward reduction is observed. A number of iridium(III) amido phosphine hydrides has been prepared The five-coordinate, 16-electron complex [Ir(H)₂N(SiMe₂CH₂PPh₂)₂], formed from [Ir(n² -C₈H₁₄)N(SiMe₂CH₂PPh₂)₂] under dihydrogen, reacts readily with neutral ligands to stereoselectively produce mer…

Subjects/Keywords: Ligands

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APA (6^th Edition):

MacNeil, P. A. (1983). Hybrid multidentate ligands : amido phosphine complexes of the Group VIII metals . (Thesis). University of British Columbia. Retrieved from http://hdl.handle.net/2429/24322

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

MacNeil, Patricia Ann. “Hybrid multidentate ligands : amido phosphine complexes of the Group VIII metals .” 1983. Thesis, University of British Columbia. Accessed February 25, 2020. http://hdl.handle.net/2429/24322.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

MacNeil, Patricia Ann. “Hybrid multidentate ligands : amido phosphine complexes of the Group VIII metals .” 1983. Web. 25 Feb 2020.

Vancouver:

MacNeil PA. Hybrid multidentate ligands : amido phosphine complexes of the Group VIII metals . [Internet] [Thesis]. University of British Columbia; 1983. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/2429/24322.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

MacNeil PA. Hybrid multidentate ligands : amido phosphine complexes of the Group VIII metals . [Thesis]. University of British Columbia; 1983. Available from: http://hdl.handle.net/2429/24322

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Rutgers University

12. Mal, Rudajit, 1983-. Development of novel bimetallic chiral complexes & formation of cyclic aminals under under Friedländer conditions.

Degree: MS, Chemistry and Chemical Biology, 2010, Rutgers University

URL: http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000053349

► The design of new chiral binuclear ligands was undertaken to address the challenge of catalyzing nucleophilic additions to simple α,β- unsaturated carbonyl compounds. The designs… (more)

Subjects/Keywords: Ligands (Biochemistry)

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APA (6^th Edition):

Mal, Rudajit, 1. (2010). Development of novel bimetallic chiral complexes & formation of cyclic aminals under under Friedländer conditions. (Masters Thesis). Rutgers University. Retrieved from http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000053349

Chicago Manual of Style (16^th Edition):

Mal, Rudajit, 1983-. “Development of novel bimetallic chiral complexes & formation of cyclic aminals under under Friedländer conditions.” 2010. Masters Thesis, Rutgers University. Accessed February 25, 2020. http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000053349.

MLA Handbook (7^th Edition):

Mal, Rudajit, 1983-. “Development of novel bimetallic chiral complexes & formation of cyclic aminals under under Friedländer conditions.” 2010. Web. 25 Feb 2020.

Vancouver:

Mal, Rudajit 1. Development of novel bimetallic chiral complexes & formation of cyclic aminals under under Friedländer conditions. [Internet] [Masters thesis]. Rutgers University; 2010. [cited 2020 Feb 25]. Available from: http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000053349.

Council of Science Editors:

Mal, Rudajit 1. Development of novel bimetallic chiral complexes & formation of cyclic aminals under under Friedländer conditions. [Masters Thesis]. Rutgers University; 2010. Available from: http://hdl.rutgers.edu/1782.1/rucore10001600001.ETD.000053349

Rutgers University

13. Steffens, Andrew Murray, 1988-. Catalytic dehydroaromatization of alkanes by pincer-ligated iridium complexes.

Degree: PhD, Chemistry and Chemical Biology, 2016, Rutgers University

URL: https://rucore.libraries.rutgers.edu/rutgers-lib/49330/

►

Further understanding of the activation of small molecules by metal complexes is an ongoing goal in organometallic chemistry, and expansion on previously reported reactions is… (more)

▼

Further understanding of the activation of small molecules by metal complexes is an ongoing goal in organometallic chemistry, and expansion on previously reported reactions is of particular interest. This thesis will discuss expansion of transfer dehydrogenation reactions, specifically multiple transfer dehydrogenation reactions of alkanes leading to aromatic products in one pot. The synthesis of the pincer catalyst used for dehydroaromatization reactions is presented along with full characterization of each step. Optimization of dehydroaromatization reactions was performed on a variety of n-alkane starting materials to maximize yield of alkylbenzene products. Kinetics and concentrations for each starting material are presented to highlight the complexity of these reactions. Despite a mechanism that would suggest otherwise, dehydroaromatization reactions surprisingly yield benzene regardless of the starting n-alkane. This interesting appearance of benzene is discussed along with yields of benzene for various n-alkanes. Mechanistic studies and DFT calculations were performed to elucidate the mechanism through which benzene is formed, and these studies show that benzene forms though a retro-ene mechanism. Attempts to limit or maximize benzene formation were performed by utilizing the information gained through the retro-ene mechanism. Expansion of dehydroaromatization reactions is discussed through multiple dehydroaromatization reactions on the same starting material. Of particular emphasis was the formation of 1,5-dimethylnaphthalene, which is a precursor to the desirable polymer polyethylene naphthalate. 1,5-dimethylnaphthalene was observed as a product from dehydroaromatization reactions, and mechanistic studies were performed to understand the mechanism for the second dehydroaromatization reaction. Attempts to maximize yield of 1,5-dimethylnaphthalene and o-pentyltoluene, which is a precursor to 1,5-dimethylnaphthalene, were performed. Further expansion of dehydroaromatization reactions is discussed through dehydroaromatization of branched alkanes to yield products not obtainable through dehydroaromatization of n-alkanes. Of particular focus is accessing p-xylene and m-xylene via dehydroaromatization. A new synthesis of p-xylene is presented using ethylene as a starting material and utilizing dehydroaromatization of 2-ethyl-1-hexene. Optimization of these reactions is also discussed.

Advisors/Committee Members: Goldman, Alan S. (chair), Roth, Heinz (internal member), Celik, Fuat (internal member), Funk, Timothy W. (outside member).

Subjects/Keywords: Ligands; Catalysts

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APA (6^th Edition):

Steffens, Andrew Murray, 1. (2016). Catalytic dehydroaromatization of alkanes by pincer-ligated iridium complexes. (Doctoral Dissertation). Rutgers University. Retrieved from https://rucore.libraries.rutgers.edu/rutgers-lib/49330/

Chicago Manual of Style (16^th Edition):

Steffens, Andrew Murray, 1988-. “Catalytic dehydroaromatization of alkanes by pincer-ligated iridium complexes.” 2016. Doctoral Dissertation, Rutgers University. Accessed February 25, 2020. https://rucore.libraries.rutgers.edu/rutgers-lib/49330/.

MLA Handbook (7^th Edition):

Steffens, Andrew Murray, 1988-. “Catalytic dehydroaromatization of alkanes by pincer-ligated iridium complexes.” 2016. Web. 25 Feb 2020.

Vancouver:

Steffens, Andrew Murray 1. Catalytic dehydroaromatization of alkanes by pincer-ligated iridium complexes. [Internet] [Doctoral dissertation]. Rutgers University; 2016. [cited 2020 Feb 25]. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/49330/.

Council of Science Editors:

Steffens, Andrew Murray 1. Catalytic dehydroaromatization of alkanes by pincer-ligated iridium complexes. [Doctoral Dissertation]. Rutgers University; 2016. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/49330/

14. Murlidaran, Sruthi. Mechanisms underlying effects of genetic variance and general anesthetics on pentameric ligand-gated ion channels.

Degree: PhD, Computational and Integrative Biology, 2018, Rutgers University

URL: https://rucore.libraries.rutgers.edu/rutgers-lib/57080/

►

Two main projects involving molecular dynamics simulation of GABAAR and a collaborative project involving simulations of GLIC receptor are presented in this thesis. The first… (more)

▼

Two main projects involving molecular dynamics simulation of GABAAR and a collaborative project involving simulations of GLIC receptor are presented in this thesis. The first project involves analyzing and comparing the conformational and functional changes between WT and K289M GABAAR receptor. The second project involves calculating binding affinity for propofol, an intravenous anesthetic, at sites identified experimentally and verified using MD simulations in GABAAR receptor. With comparatively lesser experimental knowledge for binding sites of sevoflurane, we use flooding simulation in addition to MD simulations to find exact binding sites and understand the pathway of binding. The third project involved running MD simulations of a prokaryotic pLGIC, GLIC, a bacterial proton-gated homolog, to understand how the lipid-facing M4 helix modulates channel function. Pentameric ligand-gated ion channels mediate chemical transmission of nerve signals, when an agonist binds the ECD of the channel, leading to pore opening in the TMD. While various crystal structure of these channels has provided extensive information regarding the neurotransmitter binding sites, open/close conformations, it is still challenging to understand the microscopic interaction that drives this allosteric transition between the ECD to TMD. Molecular dynamics is an effective technique in guiding us to take a closer look at the residue level interactions. Using MD, we show how the difference in electrostatic interactions at the ECD-TMD in GABAAR interface causes the channel to open in case of the WT and destabilize the open state in case of the K289M. Similar computational approaches reveal lipid penetration disrupting the interactions within the TMD helices of the 5ALA-GLIC mutant receptor which validates the reduced channel function in these receptors, as identified by experimentalists. In addition to traditional MD simulations, biased computational techniques, like AFEP helped us isolate putative binding sites, and quantify and rank binding affinities for two commonly used intravenous (Propofol) and inhalational (Sevoflurane) anesthetic, that has experimentally shown to target GABAAR receptors. Furthermore, we are able to compare and explain the protein-anesthetic interactions that cause their affinities to different binding sites in the receptor.

Advisors/Committee Members: Brannigan, Grace (chair), Martin, Joseph (internal member), Zhu, Hao (internal member), Carnevale, Vincenzo (outside member).

Subjects/Keywords: Ligands (Biochemistry)

11 more images…

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APA (6^th Edition):

Murlidaran, S. (2018). Mechanisms underlying effects of genetic variance and general anesthetics on pentameric ligand-gated ion channels. (Doctoral Dissertation). Rutgers University. Retrieved from https://rucore.libraries.rutgers.edu/rutgers-lib/57080/

Chicago Manual of Style (16^th Edition):

Murlidaran, Sruthi. “Mechanisms underlying effects of genetic variance and general anesthetics on pentameric ligand-gated ion channels.” 2018. Doctoral Dissertation, Rutgers University. Accessed February 25, 2020. https://rucore.libraries.rutgers.edu/rutgers-lib/57080/.

MLA Handbook (7^th Edition):

Murlidaran, Sruthi. “Mechanisms underlying effects of genetic variance and general anesthetics on pentameric ligand-gated ion channels.” 2018. Web. 25 Feb 2020.

Vancouver:

Murlidaran S. Mechanisms underlying effects of genetic variance and general anesthetics on pentameric ligand-gated ion channels. [Internet] [Doctoral dissertation]. Rutgers University; 2018. [cited 2020 Feb 25]. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/57080/.

Council of Science Editors:

Murlidaran S. Mechanisms underlying effects of genetic variance and general anesthetics on pentameric ligand-gated ion channels. [Doctoral Dissertation]. Rutgers University; 2018. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/57080/

Dalhousie University

15. Lavery, Christopher B. THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS.

Degree: PhD, Department of Chemistry, 2013, Dalhousie University

URL: http://hdl.handle.net/10222/37533

► In the pursuit of increasingly efficient and/or new chemical transformations, homogeneous transition metal catalysts are proving to be invaluable components of the synthetic chemist’s toolbox.… (more)

▼ In the pursuit of increasingly efficient and/or new chemical transformations, homogeneous transition metal catalysts are proving to be invaluable components of the synthetic chemist’s toolbox. Notwithstanding the many important contributions made to the area of synthetic chemistry utilizing other transition metal catalysts, palladium-catalyzed cross-coupling techniques have been demonstrated to allow for a plethora of otherwise very difficult or even impossible bond forming reactions to be realized. In this context, appropriately designed ancillary ligands, which upon binding to a metal center can influence metal-centred reactivity, have played an essential role in the advancement of palladium-catalyzed cross-coupling reactions. This thesis describes a multi-faceted approach to the identification of effective ligands for the palladium-catalyzed construction of (sp2)carbon-nitrogen and -oxygen bonds. A new series of P,O-DalPhos ligands were developed and applied in the synthesis of of N-substituted indoles via tandem palladium-catalyzed cross-coupling/cyclizations of ortho-alkynylhalo(hetero)arenes with primary amines. Notably, one P,O-DalPhos variant, OTips-DalPhos, was demonstrated to offer the broadest known substrate scope in this important class of transformations, affording a variety of structurally diverse indoles and related heterocyclic derivatives in high yields. Also described herein is the identification of the previously reported ligand BippyPhos as an extremely robust and versatile ligand in both palladium-catalyzed carbon-nitrogen and -oxygen cross-coupling applications. Indeed, the use of a Pd/BippyPhos catalyst enabled the cross-coupling of a range of (hetero)aryl (pseudo)halides with primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, with representative examples being accommodated in air. The unprecedented scope of the Pd/BippyPhos catalyst in carbon-nitrogen cross-coupling allowed for the development of two novel one-pot, two-step syntheses of N¬-aryl heterocycles from ammonia, ortho-alkynylhalo(hetero)arenes and (hetero)aryl halides through tandem N-arylation/hydroamination reactions. A marked selectivity profile was also observed for the Pd/BippyPhos catalyst and successfully exploited in the chemoselective monoarylation of substrates featuring two distinct and potentially reactive NH-containing moieties. Finally, Pd/BippyPhos mixtures served as robust and efficient catalysts for the hydroxylation of a range of (hetero)aryl halides and ortho-alkynyl(halo)heteroarenes to form phenols and phenol-derived heterocycles. Advisors/Committee Members: Dr. Bruce Arndtsen (external-examiner), Dr. Mark Stradiotto (graduate-coordinator), Dr. Laura Turculet, Dr. Kevin Grundy and Dr. Alison Thompson (thesis-reader), Dr. Mark Stradiotto (thesis-supervisor), Not Applicable (ethics-approval), Not Applicable (manuscripts), Not Applicable (copyright-release).

Subjects/Keywords: Palladium; Catalysis; Ligands

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APA (6^th Edition):

Lavery, C. B. (2013). THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS. (Doctoral Dissertation). Dalhousie University. Retrieved from http://hdl.handle.net/10222/37533

Chicago Manual of Style (16^th Edition):

Lavery, Christopher B. “THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS.” 2013. Doctoral Dissertation, Dalhousie University. Accessed February 25, 2020. http://hdl.handle.net/10222/37533.

MLA Handbook (7^th Edition):

Lavery, Christopher B. “THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS.” 2013. Web. 25 Feb 2020.

Vancouver:

Lavery CB. THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS. [Internet] [Doctoral dissertation]. Dalhousie University; 2013. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10222/37533.

Council of Science Editors:

Lavery CB. THE DEVELOPMENT AND APPLICATION OF NEW PALLADIUM CATALYSTS IN CHALLENGING C-N AND C-O BOND FORMING REACTIONS. [Doctoral Dissertation]. Dalhousie University; 2013. Available from: http://hdl.handle.net/10222/37533

16. Gwengo, Chengeto. The impact of ligand design on the coordination chemistry and properties of metal scorpionate complexes.

Degree: 2009, Marquette University

URL: https://epublications.marquette.edu/dissertations_mu/396

► The synthesis and coordination chemistry of new classes of scorpionate ligands are discussed, with the goal to discern the impact of steric and electronic modulation… (more)

▼ The synthesis and coordination chemistry of new classes of scorpionate ligands are discussed, with the goal to discern the impact of steric and electronic modulation on the coordination chemistry and properties of metal scorpionates. The scorpionate ligands were functionalized by adding bulkier alkyl substituents at selected positions of the heterocycles rings, substituting pyrazoles with other heterocycles or by replacing hydrogen at the back position of boron with aromatic groups in tris(pyrazolyl)borates. The synthesis, structures and the coordination chemistry of a series of iron (II) and iron (III) scorpionates based on third generation para-trimethylsilylphenyltris(pyrazolyl)borates, [p-Me3 SiC6 H4 B(pzx ) 3 ] are presented. The influence of pyrazolyl substituents on the spin state of iron (II) and iron (III) complexes was observed. The donor-acceptor chemistry of para-trimethylsilylphenyltris(pyrazolyl)borates in an electrochromic device will be described. The pi-stacking interactions in Fe[tBu 5 HBCB( pz )3 ]2 , with hexa-peri-hexabenzocoronenes (HBCs) tethered at the back of boron, were responsible for the unique spin characteristics of Fe[tBu5 HBCB(pz )3 ]2 . The supramolecular structures of alkali metal salts of the Janus scorpionate [HB(mtda )3 ]- with both hard nitrogen and soft sulfur donors are described. In addition, the Janus scorpionate ligand exhibits extraordinary coordination capacity and versatility binding from two to five metal cations as demonstrated by its thallium (I) salt. The second generation Janus scorpionate ligand [HB( mtdaMe ) 3 ] have been prepared and the effect of methyl substitution versus the unsubstituted first generation Janus scorpionate on the spin state of iron (II) complexes has been studied structurally by Mossbauer spectroscopy. We synthesized the tris(thioimiadzolyl)methane; HC(tim R )3 [where tim is thioimiadzolyl group and R = Me, tBu] to explore their coordination chemistry. The Lewis acid catalyzed thiol (CS-tim ) to thione (CN-tim ) isomerizations will be explained. Silver (I) complexes of tripodal tim ligands have been prepared; their solid state and solution properties have been investigated by spectroscopic methods. Owing to the multinucleating capability of new tetrakis(pyrazolyl)lutidine (pz4 lut ) ligands, bimetallic silver (I) complexes with ligand binding in a bridging mode were synthesized. The synthesis and characterization of manganese (I) and manganese (II) complexes with different coordination modes was successfully achieved. Finally, a brief introduction to bridged ligand systems with a potential for synthesis of bimetallic complexes will be discussed. Advisors/Committee Members: Gardinier, James, Haworth, Daniel, Yi, Chae.

Subjects/Keywords: Scorpionates; Ligands; Chemistry

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APA (6^th Edition):

Gwengo, C. (2009). The impact of ligand design on the coordination chemistry and properties of metal scorpionate complexes. (Thesis). Marquette University. Retrieved from https://epublications.marquette.edu/dissertations_mu/396

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Gwengo, Chengeto. “The impact of ligand design on the coordination chemistry and properties of metal scorpionate complexes.” 2009. Thesis, Marquette University. Accessed February 25, 2020. https://epublications.marquette.edu/dissertations_mu/396.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Gwengo, Chengeto. “The impact of ligand design on the coordination chemistry and properties of metal scorpionate complexes.” 2009. Web. 25 Feb 2020.

Vancouver:

Gwengo C. The impact of ligand design on the coordination chemistry and properties of metal scorpionate complexes. [Internet] [Thesis]. Marquette University; 2009. [cited 2020 Feb 25]. Available from: https://epublications.marquette.edu/dissertations_mu/396.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Gwengo C. The impact of ligand design on the coordination chemistry and properties of metal scorpionate complexes. [Thesis]. Marquette University; 2009. Available from: https://epublications.marquette.edu/dissertations_mu/396

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of KwaZulu-Natal

17. [No author]. Isothiocyanate ligand derivatives of platinum(II) terpyridines.

Degree: 2008, University of KwaZulu-Natal

URL: http://hdl.handle.net/10413/170

► The novel compounds [Pt(trpy)(NCS)]SbF6 (1) and [Pt{4'-(Ph)trpy}(NCS)]SbF6 (2) where trpy = 2,2':6',2''-terpyridine, have been synthesised and characterised by means of elemental analysis, infrared and 1H… (more)

▼ The novel compounds [Pt(trpy)(NCS)]SbF6 (1) and [Pt{4'-(Ph)trpy}(NCS)]SbF6 (2) where trpy = 2,2':6',2''-terpyridine, have been synthesised and characterised by means of elemental analysis, infrared and 1H NMR spectroscopy, and mass spectroscopy. Compounds 1 and 2 were also prepared with the labelled S13C15N¯ ion as co-ligand; their 13C and 15N NMR spectra recorded at room temperature in CD3CN show that the ambidentate ion is coordinated to the Pt atom mainly (~ 95%) through the N atom, but that a small amount of the S-bound isomer also co-exists in an acetonitrile solution. The synthesis of 1 is preceded by the isolation of yellow 1·CH3CN?Y (Y = yellow) for which the crystal structure has been determined by single crystal X-ray diffraction; this shows that the SCN¯ ion is linearly bound to the Pt atom through the N atom in the solid state, and that the cation is planar. The solvate rapidly loses acetonitrile to form maroon 1-M (M = maroon). The maroon compound exhibits 3MMLCT (metal-metal-to-ligand charge transfer) emission in the solid state as evidenced by a red-shift in the emission maximum from 653 nm at 473 K to 770 nm at 80 K. However, there are anomalous changes in the emission intensity below 200 K; this phenomenon is explained in terms of competitive emission by defect sites in the material. Interestingly, 1-M displays thermochromic behaviour (accompanied by phase changes at Ts > 473 K) that have been documented over the temperature range 80-548 K by means of photography, emission spectral and powder X-ray diffraction measurements. Compound 1-M also exhibits selective and reversible vapochromic behaviour with acetonitrile, DMF and pyridine – the solvates are yellow. We also report solvent specific changes in the emission spectra between 1-M and its acetonitrile, DMF and pyridine solvates. The thermo- and vapochromism of 1-M are linked to the making and breaking of metallophilic Pt...Pt interactions that occur when the planar cations slide in and out of different positions with respect to each other in a π-stack. Single crystals of compound 2 are isolated by desolvation of single crystals of 2·CH3CN. The single-crystal to single-crystal transformation is easily reversed by exposing 2 to vapours of acetonitrile, as confirmed by X-ray structure determinations of 2 and 2·CH3CN performed on the same single crystal. These show that the SCN¯ ion is linearly bound to the Pt atom through the N atom and that the cation is nearly planar. Significantly, there are only very small changes in the cation and anion atom positions between 2 and 2·CH3CN; thus, single crystals of 2 have a porous metal-organic structure with solvent accessible voids/channels. As such, 2 also sorbs methanol and acetone molecules from the vapour phase, the former without loss of single crystallinity, as confirmed by an X-ray crystal structure determination of 2·CH3OH. Single crystals of 2·(CH3)2CO were obtained by direct crystallization from acetone and an X-ray structure determination performed. Interestingly, a single crystal 2·(CH3)2CO… Advisors/Committee Members: Field, John S (advisor), Munro, Orde Q (advisor).

Subjects/Keywords: Platinum compounds.; Ligands.

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APA (6^th Edition):

author], [. (2008). Isothiocyanate ligand derivatives of platinum(II) terpyridines. (Thesis). University of KwaZulu-Natal. Retrieved from http://hdl.handle.net/10413/170

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

author], [No. “Isothiocyanate ligand derivatives of platinum(II) terpyridines. ” 2008. Thesis, University of KwaZulu-Natal. Accessed February 25, 2020. http://hdl.handle.net/10413/170.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

author], [No. “Isothiocyanate ligand derivatives of platinum(II) terpyridines. ” 2008. Web. 25 Feb 2020.

Vancouver:

author] [. Isothiocyanate ligand derivatives of platinum(II) terpyridines. [Internet] [Thesis]. University of KwaZulu-Natal; 2008. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10413/170.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

author] [. Isothiocyanate ligand derivatives of platinum(II) terpyridines. [Thesis]. University of KwaZulu-Natal; 2008. Available from: http://hdl.handle.net/10413/170

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Kashmir

18. Shah, Mohammad Amin. Studies on Metal complexes with Sulphur and Selenium Ligands;.

Degree: 2014, University of Kashmir

URL: http://shodhganga.inflibnet.ac.in/handle/10603/23988

►

The work presented in this thesis deals with the review of literature and incorporates the studies of Hg II TLA and Hg II MPA systems… (more)

Subjects/Keywords: Sulphur-Selenium Ligands

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APA (6^th Edition):

Shah, M. A. (2014). Studies on Metal complexes with Sulphur and Selenium Ligands;. (Thesis). University of Kashmir. Retrieved from http://shodhganga.inflibnet.ac.in/handle/10603/23988

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Shah, Mohammad Amin. “Studies on Metal complexes with Sulphur and Selenium Ligands;.” 2014. Thesis, University of Kashmir. Accessed February 25, 2020. http://shodhganga.inflibnet.ac.in/handle/10603/23988.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Shah, Mohammad Amin. “Studies on Metal complexes with Sulphur and Selenium Ligands;.” 2014. Web. 25 Feb 2020.

Vancouver:

Shah MA. Studies on Metal complexes with Sulphur and Selenium Ligands;. [Internet] [Thesis]. University of Kashmir; 2014. [cited 2020 Feb 25]. Available from: http://shodhganga.inflibnet.ac.in/handle/10603/23988.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Shah MA. Studies on Metal complexes with Sulphur and Selenium Ligands;. [Thesis]. University of Kashmir; 2014. Available from: http://shodhganga.inflibnet.ac.in/handle/10603/23988

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Johannesburg

19. Kotze, Philippus Daniel Riekert. Ligand influences on the Rh-catalysed hydroformylation reaction.

Degree: 2009, University of Johannesburg

URL: http://hdl.handle.net/10210/2500

►

M.Sc.

The main objective of the research described in this dissertation was to prepare a range of triaryl phosphine ligands having systematically changing stereo-electronic properties… (more)

▼

M.Sc.

The main objective of the research described in this dissertation was to prepare a range of triaryl phosphine ligands having systematically changing stereo-electronic properties using Grignard reagents and P-Cl derivatives. These ligands were utilised in the Rh-catalysed hydroformylation reaction in order to determine the effects of stereo-electronic properties of these ligands on the outcome of the reaction. Initially, a first series of tri-aryl phosphine ligands having methyl or ethyl groups substituted on the ortho or para position of the phenyl rings was successfully synthesised. The stereoelectronic properties of these ligands were probed by determining the P=Se coupling constants of the Se-phosphine derivatives and the CO vibrational frequencies of the Vaskatype complexes of these ligands. It was shown that the substitution of alkyl groups on the phenyl rings of the phosphine ligands resulted in the formation of more electron-rich ligands. In the Rh-catalysed hydroformylation reaction a systematic decrease in the yields of aldehydes were observed as the basicity of the phosphine ligand increased. Inspired by the outcome of the first series, a second series of tri-aryl phosphine ligands having both methyl and fluoro groups variously substituted (ortho, meta and para positions) on the phenyl rings was successfully synthesised. It was observed that the group substituted on the ortho position electronically dominated over the group substituted in the meta and para position of the phenyl rings. Substitution of fluorine atoms on the ortho position and methyl on the para position of the phenyl rings resulted in the formation of less electron-rich phosphine ligands, while the opposite substitution pattern (p-F-o-Me) resulted in the formation of more electron-rich ligands. The former caused an increase in the yields of aldehydes obtained in the Rh-catalysed hydroformylation reaction compared to triphenylphosphine. viii A third series of tri-aryl phosphine ligands having trifluoromethyl groups substituted on the ortho, meta or para positions of the phenyl rings was successfully synthesised. It was observed that substitution of the trifluoromethyl groups on the meta and para positions of the phenyl rings resulted in the formation of less electron-rich phosphine ligands, while substitution on the ortho position resulted in the formation of more electron-rich ligands. The hydroformylation reaction with these ligands followed the same trend as with the first and second series of tri-aryl phosphine ligands. A series of tri-aryl phosphine-borane adducts of the first series of phosphine ligands was also successfully synthesised using BH3·THF. These ligands were employed in the Rh-catalysed hydroformylation reaction with the aim to determine whether in situ deprotection of the phosphine-borane adducts with CO was possible. The hydroformylation results with these adducts provided yields of aldehydes similar to those of the free phosphines. This suggested that deprotection had occurred to release the free phosphine which…

Subjects/Keywords: Ligands; Hydroformylation; Catalysts

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APA (6^th Edition):

Kotze, P. D. R. (2009). Ligand influences on the Rh-catalysed hydroformylation reaction. (Thesis). University of Johannesburg. Retrieved from http://hdl.handle.net/10210/2500

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Kotze, Philippus Daniel Riekert. “Ligand influences on the Rh-catalysed hydroformylation reaction.” 2009. Thesis, University of Johannesburg. Accessed February 25, 2020. http://hdl.handle.net/10210/2500.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Kotze, Philippus Daniel Riekert. “Ligand influences on the Rh-catalysed hydroformylation reaction.” 2009. Web. 25 Feb 2020.

Vancouver:

Kotze PDR. Ligand influences on the Rh-catalysed hydroformylation reaction. [Internet] [Thesis]. University of Johannesburg; 2009. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10210/2500.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Kotze PDR. Ligand influences on the Rh-catalysed hydroformylation reaction. [Thesis]. University of Johannesburg; 2009. Available from: http://hdl.handle.net/10210/2500

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Montana State University

20. Aebly, Andrew Henry. The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations.

Degree: College of Letters & Science, 2015, Montana State University

URL: https://scholarworks.montana.edu/xmlui/handle/1/10151

► Palladium catalysis has been utilized extensively in organic chemistry for the synthesis of complex molecules. Despite its abundant use and many successful applications, there remain… (more)

Subjects/Keywords: Palladium.; Catalysis.; Ligands.

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APA (6^th Edition):

Aebly, A. H. (2015). The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations. (Thesis). Montana State University. Retrieved from https://scholarworks.montana.edu/xmlui/handle/1/10151

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Aebly, Andrew Henry. “The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations.” 2015. Thesis, Montana State University. Accessed February 25, 2020. https://scholarworks.montana.edu/xmlui/handle/1/10151.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Aebly, Andrew Henry. “The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations.” 2015. Web. 25 Feb 2020.

Vancouver:

Aebly AH. The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations. [Internet] [Thesis]. Montana State University; 2015. [cited 2020 Feb 25]. Available from: https://scholarworks.montana.edu/xmlui/handle/1/10151.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Aebly AH. The examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxdiatative transformations: Examination of chiral X-type ligands in Pd(II)-catalyzed enantioselective oxidative transformations. [Thesis]. Montana State University; 2015. Available from: https://scholarworks.montana.edu/xmlui/handle/1/10151

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Victoria

21. Paquette, Michelle Marie. Designing optically switchable multifunctional materials using photochromic spirooxazine ligands.

Degree: Dept. of Chemistry, 2013, University of Victoria

URL: http://hdl.handle.net/1828/4967

► Photoswitchable molecular materials are of interest for optical data storage, optically controlled electronics, and light-controlled molecular machines or ‗smart‘ surfaces. A promising way to incorporate… (more)

▼ Photoswitchable molecular materials are of interest for optical data storage, optically controlled electronics, and light-controlled molecular machines or ‗smart‘ surfaces. A promising way to incorporate optical switchability into materials is by using organic photochromic molecules—which convert reversibly between two forms with light—as ligands in coordination complexes. This design allows for the intimate communication between ligand and metal such that light-induced photoisomerization may be used to modulate metal-based properties. Spirooxazines, photochromic systems that photochemically isomerize between nonconjugated ring-closed spirooxazine (SO) and highly conjugated ring-opened photomerocyanine (PMC) forms, were derivatized with a phenanthroline moiety to enable the binding of transition-metal ions. Two phenanthroline–spirooxazines, an indolyl derivative and an azahomoadamantyl derivative, were investigated in the context of chemical substitution and medium effects. The ring-opened PMC forms of the spirooxazines were characterized by solid- and/or solution-state methods to extract the relative contributions of the canonical quinoidal and zwitterionic resonance forms to their molecular structure. The PMC form of the azahomoadamantyl derivative was found to exhibit significant zwitterionic character, with demonstrated sensitivity to medium polarity. The pronounced zwitterionic character was correlated with the high stability of the PMC form, high photoresponsivity, and slow thermal relaxation rates in this class of spirooxazines. The relative ligand field strengths of the SO and PMC forms of the two phenanthroline–spirooxazines were analyzed using the FT-IR and 13C NMR carbonyl signals of their molybdenum–tetracarbonyl– spirooxazine complexes. Differences in metal–ligand bonding in the SO and PMC forms were also investigated by a density functional theory fragment molecular orbital analysis. The SO form was found to be a better π-acceptor both empirically and theoretically. Lastly, the spirooxazine ligands were incorporated into electronically bistable cobalt– dioxolene redox isomers, where the low-spin-CoIII/high-spin-CoII equilibrium is sensitive to ligand field strength. Using solution-state spectroscopic methods, it was shown that the redox state of the cobalt centre could be modulated through photoisomerization of the spirooxazine ligand. As changes in cobalt redox state are associated with changes in magnetic spin state, this system forms the basis for a room-temperature photomagnetic material and highlights the powerful role of photochromic phenanthroline–spirooxazine ligands in developing photoswitchable multifunctional materials. Advisors/Committee Members: Frank, Natia L. (supervisor).

Subjects/Keywords: Photoswitchable; ligands; metal

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Paquette, M. M. (2013). Designing optically switchable multifunctional materials using photochromic spirooxazine ligands. (Thesis). University of Victoria. Retrieved from http://hdl.handle.net/1828/4967

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Paquette, Michelle Marie. “Designing optically switchable multifunctional materials using photochromic spirooxazine ligands.” 2013. Thesis, University of Victoria. Accessed February 25, 2020. http://hdl.handle.net/1828/4967.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Paquette, Michelle Marie. “Designing optically switchable multifunctional materials using photochromic spirooxazine ligands.” 2013. Web. 25 Feb 2020.

Vancouver:

Paquette MM. Designing optically switchable multifunctional materials using photochromic spirooxazine ligands. [Internet] [Thesis]. University of Victoria; 2013. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/1828/4967.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Paquette MM. Designing optically switchable multifunctional materials using photochromic spirooxazine ligands. [Thesis]. University of Victoria; 2013. Available from: http://hdl.handle.net/1828/4967

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Victoria

22. Cameron, Beth. Synthesis of novel pendant arm macrocyclic ligands as potential models for enterobactin.

Degree: Department of Chemistry, 2018, University of Victoria

URL: https://dspace.library.uvic.ca//handle/1828/9637

► A series of pendant arm tris-catecholate macrocyclic ligands were synthesized. The first, based on 1,4,7- triaminopropyl-1, 4, 7-triazacyclononane, was prepared via condensation with 2,3-dimethoxybenzoyl chloride.… (more)

▼ A series of pendant arm tris-catecholate macrocyclic ligands were synthesized. The first, based on 1,4,7- triaminopropyl-1, 4, 7-triazacyclononane, was prepared via condensation with 2,3-dimethoxybenzoyl chloride. The deprotection of the catechol moieties was achieved with boron tribromide in 80% yields. The ferric complexes were characterized by electronic absorption spectroscopy. The second series of ligands described are based on the pendant arm macrocyclic ligand, 1, 4, 7-triaminoethyl-1, 4, 7- triazacyclononane. New routes to the preparation of this ligand were investigated; the best approach used chloroacetyl chloride as the reagent in functionalizing the nitrogen atoms of the triazacyclononane ring. The ligands, 1, 4, 7-tris-((2, 3- dihydroxyphenethyl) aminoethyl)-1, 4, 7-triazacyclononane (34) and 1, 4, 7-tris-((2, 3-dihydroxybenzyl)aminoethyl)-1, 4, 7- triazacyclononane (36) were prepared through a series of acid chloride condensation reactions, followed by reduction of the amides with diborane. The mononuclear ferric complexes of compounds 34 and 36 Were prepared and characterized by uv-visible spectroscopy. Mononuclear nickel, cobalt, and copper complexes of these ligands were also characterized by uv-visible spectroscopy. The binuclear complexes, Na[NiFe(34)] and Na[NiFe(36)], were prepared and characterized by electronic absorption spectroscopy. Tris-((2, 3-dihydroxybenzylamino)ethyl) amine, tris-((2, 3- dihydroxybenzoyl)aminoethyl)amine, and tris-((2 ,3-dihydroxyphenethyl)aminoethyl)amine were prepared by Schiff base condensation reactions, or acid chloride condensation of tris-(2-aminoethyl)amine and the appropriate catecholate moiety. The ferric complexes of these ligands were prepared and characterized by uv-visible spectroscopy. The A1(III) tris-((2,3-dihydroxybenzyl)aminoethyl)amine complex was examined by nmr spectroscopy. The Ni(II), Cu(Il) and Co(III) complexes were investigated by electronic absorption spectroscopy. The rates of base hydrolysis of [Co(tacn) (en)Cl]2+ (tacn=1, 4, 7-triazacyclononane), [Co(tacn) (amp)Cl]2+ (amp=2- aminomethylpyridine), [Co(tacn) (tn)Cl]2+, ufac-I- [Co(dien) (amp)Cl]2+ (dien=l,4,7-triazaheptane), ufac-Il- [Co (dien) (amp)]2+ and [Co (bicycloN5) C1]2+ (bicycloN5=1, 5, 8, 12, 15-pentaazabicyclo [10.5.2] nonadecane), were measured using stopped flow techniques. The base hydrolysis rates (kCH, M-1s-1; [ionic strength (M)]) are 9.66 [0.1], 154 [0.1], 40.6 [0.1], 334 [0.1], 762 [0.1], and 3X103 [1.0], respectively. The rate of [NCS-] anation of [Co (bicycloN5) (OH2)]3+, and the rates of [Br-] and [NCS-] anation of [Co (tacn) (en) (OH2)]3+ were measured as a function of pH. The pKa of the coordinated water molecules are 3.8 ([Co (bicycloN5) (OH2)]3+) and 6.5 ((Co(tacn) (en) (OH2)]3+) . The anation rates increase as the pH increases, indicating a base catalysed anation reaction through the deprotonation of the coordinated amine. In the case of the [Co(tacn) (en) (OH2)]3+ complex, the rate increases as the pH increases… Advisors/Committee Members: McAuley, Alexander (supervisor).

Subjects/Keywords: Macrocyclic compounds; Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Cameron, B. (2018). Synthesis of novel pendant arm macrocyclic ligands as potential models for enterobactin. (Thesis). University of Victoria. Retrieved from https://dspace.library.uvic.ca//handle/1828/9637

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Cameron, Beth. “Synthesis of novel pendant arm macrocyclic ligands as potential models for enterobactin.” 2018. Thesis, University of Victoria. Accessed February 25, 2020. https://dspace.library.uvic.ca//handle/1828/9637.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Cameron, Beth. “Synthesis of novel pendant arm macrocyclic ligands as potential models for enterobactin.” 2018. Web. 25 Feb 2020.

Vancouver:

Cameron B. Synthesis of novel pendant arm macrocyclic ligands as potential models for enterobactin. [Internet] [Thesis]. University of Victoria; 2018. [cited 2020 Feb 25]. Available from: https://dspace.library.uvic.ca//handle/1828/9637.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Cameron B. Synthesis of novel pendant arm macrocyclic ligands as potential models for enterobactin. [Thesis]. University of Victoria; 2018. Available from: https://dspace.library.uvic.ca//handle/1828/9637

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Victoria

23. Coulter, Kevin Robert. Synthesis, characterization and metal complexation of novel pentacoordinate N4S-donor macrobicyclic ligands.

Degree: Department of Chemistry, 2018, University of Victoria

URL: https://dspace.library.uvic.ca//handle/1828/9812

► The syntheses of three structurally isomeric pentacoordinate [special characters omitted]-donor macrobicyclic ligands are reported. The isomers differ only in the identity of the two nitrogen… (more)

▼ The syntheses of three structurally isomeric pentacoordinate [special characters omitted]-donor macrobicyclic ligands are reported. The isomers differ only in the identity of the two nitrogen atoms of the cyclam ring across which the [special characters omitted] fragment ("sulphur bridge") has been linked. The first isomer, 15-Thia-1,5,8,12- tetraazabicyclo[10.5.2]nonadecane (L1), consists of a 9-membered [special characters omitted]-donor ring fused to the 14-membered 1,5,8,11-tetraazacyclotetradecane (cyclam) ring. The ligand was synthesized by a copper(II) templated ring closure followed by borohydride reduction. A novel side product (4), a monoamide derivative of (L1), was also isolated and characterized. The second isomer, 17-Thia-1,5,8,12-tetraazabicyck)[6.6.5]nonadecane (L2), consists of linking the sulphur bridge across the diagonally opposed [1,8]-nitrogens. The ligand was synthesized by cyclizing cyclam (1,4,8,11-tetraazacyclotetradecane) with thiodiglycolic acid chloride under high dilution conditions. The third isomer, 14-Thia- 1,4,8, 11-tetraazabicyclo[9.5.3]nonadecane (L3), consists of linking the sulphur bridge across the adjacent [1,5]-nitrogens of the cyclam ring. The ligand was synthesized by cyclization of 1-thia-4,8-diazacyclododecane (20) with N,N’ –bis(α-chloro amido)diaminopropane (27) which afforded the diamide derivative, 14-Thia-1,4,8,11- tetraazabicyclo[9.5.3]nonadecane-3,9-dione (30), in high yield. Reduction of 30 with diborane gave the third structural isomer, (L3). A novel, convenient synthesis of 1-thia-4,8-diazacyclododecane-3,9-dione (23) from diaminopropane and thiodiglycolic acid chloride was developed. It was shown that high dilution conditions were necessary to obtain high product yields. The nature of the product obtained from reduction of 23 was shown to depend on the conditions used. In the presence of excess borane and methanol, the major product was a boron complex of the reduced ligand. Several changes to the conditions used avoided production of the boron complex and yielded the intended product (20) in sufficient quantity. The parent 1-Thia-4,7-diazacyclononane ([9][special characters omitted]) and 1,4,8,11- tetraazacyclotetradecane ([14][special characters omitted]) ligands exhibit first order coupling behaviour as a result of time averaging of molecular motions. However, the ambient temperature [special characters omitted] spectrum of the [9][special characters omitted] bicyclic free ligand (L1) exhibited second-order couplings and line broadening indicative of an exchange process. This result indicates that the rigidity of the macrobicyclic structure has hindered certain molecular motions. The variable-temperature [special characters omitted] spectra of (L1) were recorded in deuterated chloroform. It was found that the geminal coupling (> 15 Hz) of the [special characters omitted] (propylene fragment) methylene group approached 0 Hz as the temperature was raised beyond 40°C. It is believed that nitrogen inversion processes are… Advisors/Committee Members: McAuley, Alexander (supervisor).

Subjects/Keywords: Ligands; Macrocyclic compounds

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Coulter, K. R. (2018). Synthesis, characterization and metal complexation of novel pentacoordinate N4S-donor macrobicyclic ligands. (Thesis). University of Victoria. Retrieved from https://dspace.library.uvic.ca//handle/1828/9812

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Coulter, Kevin Robert. “Synthesis, characterization and metal complexation of novel pentacoordinate N4S-donor macrobicyclic ligands.” 2018. Thesis, University of Victoria. Accessed February 25, 2020. https://dspace.library.uvic.ca//handle/1828/9812.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Coulter, Kevin Robert. “Synthesis, characterization and metal complexation of novel pentacoordinate N4S-donor macrobicyclic ligands.” 2018. Web. 25 Feb 2020.

Vancouver:

Coulter KR. Synthesis, characterization and metal complexation of novel pentacoordinate N4S-donor macrobicyclic ligands. [Internet] [Thesis]. University of Victoria; 2018. [cited 2020 Feb 25]. Available from: https://dspace.library.uvic.ca//handle/1828/9812.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Coulter KR. Synthesis, characterization and metal complexation of novel pentacoordinate N4S-donor macrobicyclic ligands. [Thesis]. University of Victoria; 2018. Available from: https://dspace.library.uvic.ca//handle/1828/9812

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Victoria

24. Ingham, Alison Mary. The synthesis and characterisation of macrocrylic ligands with N, O and S donor atoms and related transmission metal complexes of these ligands.

Degree: Department of Chemistry, 2018, University of Victoria

URL: https://dspace.library.uvic.ca//handle/1828/9707

► The ligand 1-oxa-4,8-diazacyclodecane ([10]aneN2O) was synthesised, along with the [special characters omitted] complexes. Bis-ligand complexes are formed with facial coordination of the ligand to the… (more)

▼ The ligand 1-oxa-4,8-diazacyclodecane ([10]aneN2O) was synthesised, along with the [special characters omitted] complexes. Bis-ligand complexes are formed with facial coordination of the ligand to the transition metals, with two nitrogen donors from each ligand forming an equatorial plane around the metal ion. The crystal structure of [special characters omitted] was determined, as is described. The copper(II), nickel(II) and palladium(II) complexes have been characterised by FAB MS, electronic spectroscopy, elemental analysis and where possible by NMR and EPR spectroscopy. The nickel(II) and copper(II) complexes have distorted octahedral geometries, while the palladium(II) complex has square planar geometry with no observable axial interaction from the ether donors. The redox characteristics of the complexes formed have been determined, and are described within. The synthesis of the novel tricyclic ligand, 7,16-dioxa-1,4,10,13- tetraazatricyclo[11.5.3.3]octadecane [special characters omitted] is described. The [special characters omitted] conplex has been synthesised and characterised. The complex gives an unusually stable [special characters omitted] complex compared to complexes where a similar donor set is present A novel template synthesis was utilised to synthesise the bicyclic ligand 1,2-bis(1-oxa-5,8-diazacyclodecanyl)ethane ([special characters omitted] earmuff). This synthesis involved reaction of secondary amines which are coordinated to a copper(II) ion, a method which to our knowledge has not been used before in the synthesis of macrocyclic ligands. The copper(II) complex synthesised during this reaction has been characterised, and the redox reactions have been examined. The synthesis of 17-oxa-1,4,8,11-tetraazabicyclo[6.6.5]tetradecane (bicyclo[12-12] [special characters omitted]) is reported. Copper(II) and nickeI(II) complexes of this ligand have been synthesised and characterised. The chloride ion substitution reaction of [Ni(bicyclo[12-12] [special characters omitted] has been examined. The reaction was found to have an inverse dependence on the acid concentration. A tentative mechanism has been proposed to explain the origin of the acid dependence. The equilibrium constant for this reaction, determined by visible spectrophotometry, was found to be [special characters omitted]. The cobalt(III) bis-ligand complex of the previously synthesised ligand, 8-aza-1,5- dithiacyclodecane ([special characters omitted]) was synthesised. Under the conditions used, two isomers were formed - a facially coordinate bis-ligand complex where the equatorial plane is defined by two sulfur and two nitrogen donors, and a more symmetrical isomer where all four sulfur donors are coordinated equatorially. Isomerisation of the unsymmetrical isomer to the symmetrical isomer occurs in solution. The [special characters omitted] complexes of the ligand 1,2-bis(8-aza-1,5-dithiacycIodecanyI)ethane ([special characters omitted] earmuff) were synthesised and characterised. The ligand coordinates to… Advisors/Committee Members: McAuley, Alexander (supervisor).

Subjects/Keywords: Ligands; Macrocrylic compounds

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Ingham, A. M. (2018). The synthesis and characterisation of macrocrylic ligands with N, O and S donor atoms and related transmission metal complexes of these ligands. (Thesis). University of Victoria. Retrieved from https://dspace.library.uvic.ca//handle/1828/9707

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Ingham, Alison Mary. “The synthesis and characterisation of macrocrylic ligands with N, O and S donor atoms and related transmission metal complexes of these ligands.” 2018. Thesis, University of Victoria. Accessed February 25, 2020. https://dspace.library.uvic.ca//handle/1828/9707.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Ingham, Alison Mary. “The synthesis and characterisation of macrocrylic ligands with N, O and S donor atoms and related transmission metal complexes of these ligands.” 2018. Web. 25 Feb 2020.

Vancouver:

Ingham AM. The synthesis and characterisation of macrocrylic ligands with N, O and S donor atoms and related transmission metal complexes of these ligands. [Internet] [Thesis]. University of Victoria; 2018. [cited 2020 Feb 25]. Available from: https://dspace.library.uvic.ca//handle/1828/9707.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Ingham AM. The synthesis and characterisation of macrocrylic ligands with N, O and S donor atoms and related transmission metal complexes of these ligands. [Thesis]. University of Victoria; 2018. Available from: https://dspace.library.uvic.ca//handle/1828/9707

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of California – San Diego

25. Weinstein, Cory. Development and Reactivity Studies of Highly Ambiphilic Carbenes.

Degree: Chemistry, 2018, University of California – San Diego

URL: http://www.escholarship.org/uc/item/57t561ss

► Since their seminal isolation as stable species in 1988, carbenes have become indispensable ligands across a myriad of fields within chemistry. The origin of their… (more)

Subjects/Keywords: Chemistry; Carbenes; Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Weinstein, C. (2018). Development and Reactivity Studies of Highly Ambiphilic Carbenes. (Thesis). University of California – San Diego. Retrieved from http://www.escholarship.org/uc/item/57t561ss

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Weinstein, Cory. “Development and Reactivity Studies of Highly Ambiphilic Carbenes.” 2018. Thesis, University of California – San Diego. Accessed February 25, 2020. http://www.escholarship.org/uc/item/57t561ss.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Weinstein, Cory. “Development and Reactivity Studies of Highly Ambiphilic Carbenes.” 2018. Web. 25 Feb 2020.

Vancouver:

Weinstein C. Development and Reactivity Studies of Highly Ambiphilic Carbenes. [Internet] [Thesis]. University of California – San Diego; 2018. [cited 2020 Feb 25]. Available from: http://www.escholarship.org/uc/item/57t561ss.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Weinstein C. Development and Reactivity Studies of Highly Ambiphilic Carbenes. [Thesis]. University of California – San Diego; 2018. Available from: http://www.escholarship.org/uc/item/57t561ss

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Boston College

26. Joe, Candice Lee. Design and Synthesis of Scaffolding Ligands for Regio- and Stereoselective Hydroformylation.

Degree: PhD, Chemistry, 2014, Boston College

URL: http://dlib.bc.edu/islandora/object/bc-ir:103550

► Chapter 1. The use of directing groups is a powerful way to control selectivity in organic chemistry. Due to their ability to install new functionality… (more)

▼ Chapter 1. The use of directing groups is a powerful way to control selectivity in organic chemistry. Due to their ability to install new functionality in a reliable fashion, directing groups have had a profound impact on stereoselective, site-selective, and regioselective transformations. More recently, catalytic directing groups have been developed and utilized in a variety of metal-catalyzed transformations, including C-H activation and hydroacylation, and have the potential to be more broadly applied to other transformations. Chapter 2. Catalytic directing groups have recently been designed for hydroformylation. Based on the design of racemic scaffolding ligand 2.5, enantioenriched ligand 2.42 was synthesized for the asymmetric hydroformylation of para-methoxyphenyl (PMP) protected allylic amines. Under mild conditions, a variety of 1,2-disubstituted olefins underwent directed hydroformylation to afford the proximal β-amino alcohol products in good yields and excellent enantioselectivities. The substrate scope has been extended to electronically modified allylic anilines. A modest resonance effect was seen upon the aniline substrate binding to the ligand, which, in turn, manifested in the hydroformylation reaction results. Thus the first enantioselective reaction performed with a catalytic directing group was demonstrated. Chapter 3. Ligand 3.67 was developed, which promotes aldehyde formation on the distal olefinic carbon relative to the directing functionality on the substrate. This is in contrast to other phosphorus-based directing groups that have been successful at placing the aldehyde on the proximal olefinic carbon. Ligand 3.67 has been applied to the diastereoselective hydroformylation of homoallylic alcohols to afford δ-lactones selectively. Altering the distance between the alcohol and olefin revealed that homoallylic alcohols afford the distal lactone with the highest levels of regioselectivity. Taken together with previous examples of proximal-selective hydroformylation, these results being to more fully address the challenge of controlling regioselectivity in hydroformylation. Chapter 4. The harvesting of energy from light to power chemical transformations is an underdeveloped area. Utilizing p-type silicon nanowires (SiNWs) as a photocathode, the photoelectrochemical carboxylation of aromatic ketones has been developed to afford α-hydroxy carboxylic acids. Utilizing low operating potentials, the direct reduction of carbon dioxide (CO2) is avoided. Highlighting the synthetic utility of this transformation, two precursors to the NSAID compounds ibuprofen and naproxen were synthesized using CO2, and abundant C1 feedstock, and light, a crucial source of energy in nature. Advisors/Committee Members: Kian L. Tan (Thesis advisor).

Subjects/Keywords: Hydroformylation; Scaffolding Ligands

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Joe, C. L. (2014). Design and Synthesis of Scaffolding Ligands for Regio- and Stereoselective Hydroformylation. (Doctoral Dissertation). Boston College. Retrieved from http://dlib.bc.edu/islandora/object/bc-ir:103550

Chicago Manual of Style (16^th Edition):

Joe, Candice Lee. “Design and Synthesis of Scaffolding Ligands for Regio- and Stereoselective Hydroformylation.” 2014. Doctoral Dissertation, Boston College. Accessed February 25, 2020. http://dlib.bc.edu/islandora/object/bc-ir:103550.

MLA Handbook (7^th Edition):

Joe, Candice Lee. “Design and Synthesis of Scaffolding Ligands for Regio- and Stereoselective Hydroformylation.” 2014. Web. 25 Feb 2020.

Vancouver:

Joe CL. Design and Synthesis of Scaffolding Ligands for Regio- and Stereoselective Hydroformylation. [Internet] [Doctoral dissertation]. Boston College; 2014. [cited 2020 Feb 25]. Available from: http://dlib.bc.edu/islandora/object/bc-ir:103550.

Council of Science Editors:

Joe CL. Design and Synthesis of Scaffolding Ligands for Regio- and Stereoselective Hydroformylation. [Doctoral Dissertation]. Boston College; 2014. Available from: http://dlib.bc.edu/islandora/object/bc-ir:103550

Nelson Mandela Metropolitan University

27. Mukiza, Janvier. Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups.

Degree: Faculty of Science, 2016, Nelson Mandela Metropolitan University

URL: http://hdl.handle.net/10948/12308

► The chemistry of rhenium has received considerable interest due to its versatility in various catalytic applications, fixation and especially the potential use of 186Re and… (more)

▼ The chemistry of rhenium has received considerable interest due to its versatility in various catalytic applications, fixation and especially the potential use of 186Re and 188Re radionuclides in nuclear medicine. This study investigates the synthesis and characterisation of rhenium complexes with potentially multidentate ligands containing the amino, imino, hydroxyl and thiol groups. It reports new rhenium complexes in the +1, +3, +4 and +5 oxidation states, which display structural diversity, from monomers to ligand-bridged dimers as well as metal-metal multiply bonded dimers. The reaction of orotic acid (H2oa) and 2-mercapto-orotic acid (H2moa) with trans- [ReOX3(PPh3)2] (X = Cl, Br) were studied and led to the formation of ligand-bridged dimers with metal-metal multiple bonds i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-X)(μ-O)(μ-oa)[Re2 IVX2(OiPr)(PPh3)2] and (μ-Cl)(μ-O)(μ-moa)2[Re(PPh3)]2. The reaction of H2oa with [ReO2(py)4]Cl, [Re(dab)Br3(PPh3)2] (H2dab = 1,2- diaminobenzene) and [Re(CO)5Cl] were also studied and monomeric complexes [ReO(py)2(OEt)(oa)], [Re(dab)Br(oa)(PPh3)2] and (Ph4P)[Re(CO)3(H2O)(oa)] were isolated. The treatment of 5-amino-orotic acid (H2aoa) with [ReOBr3(PPh3)2] led to dimers with metal-metal triple bonds ReIV≡ReIV i.e. (μ-Br)(μ-O)(μ-oa)[Re2 IVBr(OEt)2(PPh3)2], (μ-Br)(μ-O)(μ-oa)[Re2 IVBr2(OiPr)(PPh3)2], as well as the monomer [ReV(apd)Br(aoa)(PPh3)2] (apd2− = 5-imidopyrimidine-2,4-dione). The chelating ligand 5-aminopyrimidine-2,4-dione (H2apd) was formed by oxorhenium(V)-catalysed decarboxylation of 5-amino-orotic acid (H2aoa) (see Scheme 1). The reaction of the Schiff base derivative of 5-amino-ortic acid, salicylimine-orotic acid (H2soa), with trans-[ReOI2(OEt)(PPh3)2] in ethanol was also investigated and led to the formation of the rhenium(III) complex salt [Re(coa)I(PPh3)2]I [Hcoa = 5-(2- hydroxybenzylideneamino)pyrimidine-2,4(1H,3H)-dione]. The chelating Hcoa is also formed from the oxorhenium(V)-catalysed decarboxylation of H2soa and coordinates to the rhenium(III) ion as a monoanionic tridentate N,O,O-donor chelate via the phenolate and ketonic oxygens, and the imino nitrogen atom. However, decarboxylation of H2soa was not observed in its reaction with [ReOCl3(PPh3)2], which led to the isolation of [ReOCl(soa)(PPh3)]. The reaction of the carboxamide derivative of 5-aminoorotic acid, 5-(5-aminopyrimidine-2,4(1H,3H)- dioxamido)-1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-carboxylic acid (H2ampa) with [Re(CO)5Cl] in ethanol led to the formation of a zwitterionic rhenium(I) complex [Re(CO)3(H2O)(amef)] [amef = {5-(5-ammoniumpyrimidine-2,4(1H,3H)-dioxamido)- 1,2,3,6-tetrahedro-2,6-dioxopyrimidine-4-ethylformate}]. The chelating ion amef was formed from the combined tricarbonylrhenium(I)-catalysed esterification and aminoprotonation of H2ampa (see Scheme 1) and coordinates to the fac-[Re(CO)3]+ core as a dianionic bidentate N,N-donor chelate via the amido nitrgens.

Subjects/Keywords: Rhenium; Thiols; Ligands

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APA (6^th Edition):

Mukiza, J. (2016). Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups. (Thesis). Nelson Mandela Metropolitan University. Retrieved from http://hdl.handle.net/10948/12308

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16^th Edition):

Mukiza, Janvier. “Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups.” 2016. Thesis, Nelson Mandela Metropolitan University. Accessed February 25, 2020. http://hdl.handle.net/10948/12308.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7^th Edition):

Mukiza, Janvier. “Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups.” 2016. Web. 25 Feb 2020.

Vancouver:

Mukiza J. Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups. [Internet] [Thesis]. Nelson Mandela Metropolitan University; 2016. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/10948/12308.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Mukiza J. Rhenium complexes with pontentially multidentate ligands containing the amino, imino, hydroxy and thiol groups. [Thesis]. Nelson Mandela Metropolitan University; 2016. Available from: http://hdl.handle.net/10948/12308

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

University of Oklahoma

28. Jozwiuk, Anna Maria. Imitating Nature: The Effects of Asymmetry and Strain on Copper and Iron Complexes with Schiff Base Ligands.

Degree: PhD, 2013, University of Oklahoma

URL: http://hdl.handle.net/11244/319347

► In another study, the aspect of geometrical strain was investigated. The distorted copper(II) complexes [CuL5-gem] and [CuL5-ortho] (L5-gem = Pseudo-gem-N,N'-bissalicylidene-4,15-diamino[2.2]paracyclophane and L5-ortho = Pseudo-ortho-N,N'-bissalicylidene-4,16-diamino[2.2]paracyclophane) which… (more)

Subjects/Keywords: Metalloenzymes; Ligands; Metalloproteins

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Jozwiuk, A. M. (2013). Imitating Nature: The Effects of Asymmetry and Strain on Copper and Iron Complexes with Schiff Base Ligands. (Doctoral Dissertation). University of Oklahoma. Retrieved from http://hdl.handle.net/11244/319347

Chicago Manual of Style (16^th Edition):

Jozwiuk, Anna Maria. “Imitating Nature: The Effects of Asymmetry and Strain on Copper and Iron Complexes with Schiff Base Ligands.” 2013. Doctoral Dissertation, University of Oklahoma. Accessed February 25, 2020. http://hdl.handle.net/11244/319347.

MLA Handbook (7^th Edition):

Jozwiuk, Anna Maria. “Imitating Nature: The Effects of Asymmetry and Strain on Copper and Iron Complexes with Schiff Base Ligands.” 2013. Web. 25 Feb 2020.

Vancouver:

Jozwiuk AM. Imitating Nature: The Effects of Asymmetry and Strain on Copper and Iron Complexes with Schiff Base Ligands. [Internet] [Doctoral dissertation]. University of Oklahoma; 2013. [cited 2020 Feb 25]. Available from: http://hdl.handle.net/11244/319347.

Council of Science Editors:

Jozwiuk AM. Imitating Nature: The Effects of Asymmetry and Strain on Copper and Iron Complexes with Schiff Base Ligands. [Doctoral Dissertation]. University of Oklahoma; 2013. Available from: http://hdl.handle.net/11244/319347

Rutgers University

29. Chie, Yu-Ming, 1980-. Synthesis of new phosphorus ligands for regioselective hydroformylation:.

Degree: MS, Chemistry, 2010, Rutgers University

URL: http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052101

► Tetraphosphorous ligands with enhanced chelating ability through multiple chelating modes and increased local phosphorus concentration can provide great regioselectivity in Rh/Ligand hydroformylation system. Here we… (more)

▼ Tetraphosphorous ligands with enhanced chelating ability through multiple chelating modes and increased local phosphorus concentration can provide great regioselectivity in Rh/Ligand hydroformylation system. Here we report the synthesis of a series of pyrrole-based tetraphosphorus ligands were synthesized with introducing different functional groups into 3, 3', 5, 5'-positions of the biphenyl, and their applications to the hydroformylation of internal olefins, 1, 5-hexadiene, styrene and its derivatives, and alkyl acrylates. Internal olefins are cheaper and more readily available feedstock than terminal olefins, the development of highly selective and active isomerization-hydroformylation catalysts for internal olefins is of great importance from economic and energy points of view. In particular, the alkyl-substituted tetraphosphorous ligands gave the best results (for 2-octene, n: i up to 207, for 2-hexene, n: i up to 362). Double hydroformylation of 1, n-diolefins is a convenient method to produce dialdehydes. The hydroformylation of 1, 5- hexadiene can be achieved with essentially high regioselectivity (linear selectivity is up to 98%). Styrene and its derivatives prefer the branched aldehydes under the hydro-formylation conditions. However, the linear aldehydes can also be widely used for the production of detergents and plasticizers and important intermediates. Our studies on the hydroformylation of styrene and its derivatives achieved unprecedented high linear selectivity (l/b up to 22 for styrene). Hydroformylation of alkyl acrylate produces 1, 3- and1, 4-bifunctional compounds, which can be further converted into synthetically useful intermediates. Alkyl acrylates have been hydroformylated to the linear aldehydes with high regioselectivity (linear/branch > 99/1) and extraordinarily high average turnover frequencies (up to 5400 h 1) by using a rhodium complex with a tetraphosphorus ligand. The result is in sharp contrast to the most of other processes that favor production of the branched aldehyde (typically > 95% branched for most Rh-catalyzed reaction systems). Advisors/Committee Members: Chie, Yu-Ming, 1980- (author), Zhang, Xumu (chair), Seidel, Daniel (internal member), Jimenez, Leslie (internal member).

Subjects/Keywords: Ligands – Synthesis; Hydroformylation

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Chie, Yu-Ming, 1. (2010). Synthesis of new phosphorus ligands for regioselective hydroformylation:. (Masters Thesis). Rutgers University. Retrieved from http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052101

Chicago Manual of Style (16^th Edition):

Chie, Yu-Ming, 1980-. “Synthesis of new phosphorus ligands for regioselective hydroformylation:.” 2010. Masters Thesis, Rutgers University. Accessed February 25, 2020. http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052101.

MLA Handbook (7^th Edition):

Chie, Yu-Ming, 1980-. “Synthesis of new phosphorus ligands for regioselective hydroformylation:.” 2010. Web. 25 Feb 2020.

Vancouver:

Chie, Yu-Ming 1. Synthesis of new phosphorus ligands for regioselective hydroformylation:. [Internet] [Masters thesis]. Rutgers University; 2010. [cited 2020 Feb 25]. Available from: http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052101.

Council of Science Editors:

Chie, Yu-Ming 1. Synthesis of new phosphorus ligands for regioselective hydroformylation:. [Masters Thesis]. Rutgers University; 2010. Available from: http://hdl.rutgers.edu/1782.2/rucore10001600001.ETD.000052101

Rutgers University

30. Zheng, Xin, 1985-. Synthesis and development of phosphorus ligands in the application of rhodium-catalyzed hydroformylation.

Degree: PhD, Chemistry and Chemical Biology, 2015, Rutgers University

URL: https://rucore.libraries.rutgers.edu/rutgers-lib/48744/

►

Rhodium-catalyzed hydroformylation reaction is one of the most powerful homogeneous catalytic processes in the synthesis of aldehydes that can be widely applied in pharmaceuticals and… (more)

▼

Rhodium-catalyzed hydroformylation reaction is one of the most powerful homogeneous catalytic processes in the synthesis of aldehydes that can be widely applied in pharmaceuticals and fine chemicals. The design and synthesis phosphorus ligands combine with rhodium precursor used as catalysts is essentially important in the development of this reaction. This dissertation mainly focuses on the design, synthesis and application of efficient phosphorus ligands in rhodium-catalyzed hydroformylation. Asymmetric hydroformylation reaction (AHF), especially rhodium-catalyzed AHF has played a central role to construct chiral aldehydes in only one step. Although tons of chiral phosphorus ligands have been reported, few of them exhibited practicable enantioselectivities and regioselectivities. We report a new family of highly tunable bisphospholane ligands in the application of series of terminal and internal olefins, affording up to 88% for styrene derivatives, 93% ee for vinyl acetate derivatives, 93% ee for dihydrofuran and 96% for dihyropyrrole. A systematic screening different substituents on the ligand showed that ortho chloride on phenyl moiety was the successful structure, achieving the highest regio- and enantioselectivity. To expand the scope of substrates, especially the more challenging 1,1-disubstituted olefins, we first report the asymmetric hydroformylation of 1,1-disubstituted allylphthalimides by employing chiral ligand 1,2-bis[(2S,5S)-2,5-diphenylphospholano]ethane [(S,S)-Ph-BPE] to yield a series of beta-3-aminoaldehydes with up to 95% enantioselectivity. This asymmetric procedure provides an efficient alternative route to prepare chiral beta-3-amino acids and alcohols that are key structural elements of beta-aminobutyric acid. Hydroaminomethylation is the tandem reaction of hydroformylation/hydrogenation. This efficient reaction is utilized to build nitrogen-containing compounds, which are interesting in pharmaceutics and fine chemicals. In this chapter, we disclose the synthesis of 4-aryl-2,3-dihyropyrrole derivatives by rhodium-catalyzed intramolecular hydrominometylation reaction with up to 99% yield.

Advisors/Committee Members: Zhang, Xumu (chair).

Subjects/Keywords: Hydroformylation; Ligands; Rhodium

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6^th Edition):

Zheng, Xin, 1. (2015). Synthesis and development of phosphorus ligands in the application of rhodium-catalyzed hydroformylation. (Doctoral Dissertation). Rutgers University. Retrieved from https://rucore.libraries.rutgers.edu/rutgers-lib/48744/

Chicago Manual of Style (16^th Edition):

Zheng, Xin, 1985-. “Synthesis and development of phosphorus ligands in the application of rhodium-catalyzed hydroformylation.” 2015. Doctoral Dissertation, Rutgers University. Accessed February 25, 2020. https://rucore.libraries.rutgers.edu/rutgers-lib/48744/.

MLA Handbook (7^th Edition):

Zheng, Xin, 1985-. “Synthesis and development of phosphorus ligands in the application of rhodium-catalyzed hydroformylation.” 2015. Web. 25 Feb 2020.

Vancouver:

Zheng, Xin 1. Synthesis and development of phosphorus ligands in the application of rhodium-catalyzed hydroformylation. [Internet] [Doctoral dissertation]. Rutgers University; 2015. [cited 2020 Feb 25]. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/48744/.

Council of Science Editors:

Zheng, Xin 1. Synthesis and development of phosphorus ligands in the application of rhodium-catalyzed hydroformylation. [Doctoral Dissertation]. Rutgers University; 2015. Available from: https://rucore.libraries.rutgers.edu/rutgers-lib/48744/

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