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You searched for subject:(weakly coordinating anions). Showing records 1 – 3 of 3 total matches.

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Texas A&M University

1. Press, Loren Paul. High-Turnover C-H Borylation of Arenes with (POCOP) Iridium Complexes, The Synthesis of Group 9/10 (POCS) Complexes and the Study of Triflyloxy-Substituted Carboranes.

Degree: PhD, Chemistry, 2016, Texas A&M University

Over the last century, transition metal-catalyzed C-H functionalization has emerged as one of the most important topics in synthetic chemistry. One type of C-H functionalization, known as C-H borylation, generates organoboron reagents directly from hydrocarbon substrates. The synthetic utility of organoboron compounds is well established and numerous systems have been developed for the catalytic C-H borylation of alkyl and aromatic substrates since the reaction was first conceived over 20 years ago, yet catalysts that support high TONs remain limited to a handful of examples. Here we present highly active POCOP iridium complexes for the catalytic C-H borylation of arenes. In favorable cases, TONs exceeding 10,000 have been observed. The synthesis and isolation of multiple complexes potentially relevant to catalysis permitted examination of several key elementary reactions. We found C-H activation at Ir(I) here is in contrast to the olefin-free catalysis with state-of-the-art Ir complexes supported by neutral bidentate ligands, where the C-H activating step is understood to involve trivalent Ir-boryl intermediates. Next, we investigated the stoichiometric reactivity of a (POCOP)Ir(boryl)2 complex with various small molecules under thermolytic conditions. Transition metalboryl complexes are ubiquitous in the literature and have been identified as key intermediates in several critical chemical transformations including C-H borylation and hydroborylation chemistries. The (POCOP)Ir(boryl)2 complex was found to undergo several stoichiometric transformations including reduction of CO2 to CO, 1,2- diborylation of ethylene and the selective protonation of one boryl ligand. The synthesis and characterization of novel POCS pincer complexes of nickel, palladium and iridium are described. The modular design of the POCS pincer ligand allowed the exploration of monomeric and bridging ligand designs akin to PNN and PCN complexes. The selective B-H functionalization of the mono-anionic carborane [HCB11H11]^– with one or three triflyloxy (OTf) groups is described. The mono-triflyloxy substituted carborane can be halogenated to give pentabromo and decachloro derivatives with preservation of the B–OTf linkage. The use of [HCB11Cl10OTf]^– as a weakly coordinating anion is demonstrated. Advisors/Committee Members: Ozerov, Oleg V. (advisor), Darensbourg, Donald J. (committee member), Hall, Michael B. (committee member), Lutkenhaus, Jodie L. (committee member).

Subjects/Keywords: C-H functionalization; C-H activation; borylation; POCOP; iridium; POCS; triflyloxy; carboranes; weakly coordinating anions

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

APA (6th Edition):

Press, L. P. (2016). High-Turnover C-H Borylation of Arenes with (POCOP) Iridium Complexes, The Synthesis of Group 9/10 (POCS) Complexes and the Study of Triflyloxy-Substituted Carboranes. (Doctoral Dissertation). Texas A&M University. Retrieved from http://hdl.handle.net/1969.1/158080

Chicago Manual of Style (16th Edition):

Press, Loren Paul. “High-Turnover C-H Borylation of Arenes with (POCOP) Iridium Complexes, The Synthesis of Group 9/10 (POCS) Complexes and the Study of Triflyloxy-Substituted Carboranes.” 2016. Doctoral Dissertation, Texas A&M University. Accessed October 23, 2019. http://hdl.handle.net/1969.1/158080.

MLA Handbook (7th Edition):

Press, Loren Paul. “High-Turnover C-H Borylation of Arenes with (POCOP) Iridium Complexes, The Synthesis of Group 9/10 (POCS) Complexes and the Study of Triflyloxy-Substituted Carboranes.” 2016. Web. 23 Oct 2019.

Vancouver:

Press LP. High-Turnover C-H Borylation of Arenes with (POCOP) Iridium Complexes, The Synthesis of Group 9/10 (POCS) Complexes and the Study of Triflyloxy-Substituted Carboranes. [Internet] [Doctoral dissertation]. Texas A&M University; 2016. [cited 2019 Oct 23]. Available from: http://hdl.handle.net/1969.1/158080.

Council of Science Editors:

Press LP. High-Turnover C-H Borylation of Arenes with (POCOP) Iridium Complexes, The Synthesis of Group 9/10 (POCS) Complexes and the Study of Triflyloxy-Substituted Carboranes. [Doctoral Dissertation]. Texas A&M University; 2016. Available from: http://hdl.handle.net/1969.1/158080


EPFL

2. Raabe, Ines. Salts of electrophilic cations and Lewis acid-base adducts with weakly coordinating anions: synthesis, characterization and quantum chemical calculations.

Degree: 2007, EPFL

During the last decades, weakly coordinating anions (WCAs) have become a field of great interest both in basic and applied chemistry, as – if compared to "normal" classical anions like Cl- or SO42- – they have a lot of unique and unusual properties, such as high solubility in low dielectric media (like CH2Cl2 or toluene), "pseudo gas phase conditions" in condensed phases and the stabilization of strong electrophilic cations as well as of weakly bound and low charged complexes. Within the present thesis, several contributions to the chemistry of WCAs were made: Based on quantum chemical calculations, the stability of the most widely used WCAs have been investigated, using parameters such as the fluoride ion affinity (FIA), partial charges or frontier orbital energies. One class of the WCAs, the poly- and perfluorinated alkoxyaluminates of the type [Al(ORF)4]- and [(RFO)3Al-F-Al(ORF)3]-, has been used to investigate weakly bound Ag(P4S3) Lewis acid-base adducts and electrophilic cations: When the silver salts of fluorinated alkoxyaluminates are reacted with P4S3, different structure types are found for the adducts, depending on the anion used. The dynamics of these complexes has been explored by different spectroscopic methods (IR, Raman, MAS-NMR, NMR in solution) and X-ray diffraction. The first structurally characterized trihalocarbenium ions CI3+ as salts of different aluminates have been prepared and fully characterized using various spectroscopic techniques, e.g. NMR and vibrational spectroscopy, as well as single-crystal diffraction. The Lewis acidities of the halocarbenium ions have been investigated both on experimental and theoretical grounds and they have been compared to those of the isoelectronic haloboranes. The NO2+ salt of the [Al(OC(CF3)3)4]- anion has been synthesized by a metathesis reaction. It has been reacted with P4 in order to obtain naked phosphorus cations Px+. Another project was the synthesis and characterization of the tetraalkylammonium salts of the [Al(ORF)4]- anions, a promising class of substances for the use in electrochemical applications in non-polar solvents. All subjects treated experimentally within this thesis have been accompanied by quantum chemical calculations. Advisors/Committee Members: Krossing, Ingo.

Subjects/Keywords: weakly coordinating anions; halocarbenium ions; Lewis acid-base adducts; quantum chemical calculations

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

APA (6th Edition):

Raabe, I. (2007). Salts of electrophilic cations and Lewis acid-base adducts with weakly coordinating anions: synthesis, characterization and quantum chemical calculations. (Thesis). EPFL. Retrieved from http://infoscience.epfl.ch/record/103748

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

Chicago Manual of Style (16th Edition):

Raabe, Ines. “Salts of electrophilic cations and Lewis acid-base adducts with weakly coordinating anions: synthesis, characterization and quantum chemical calculations.” 2007. Thesis, EPFL. Accessed October 23, 2019. http://infoscience.epfl.ch/record/103748.

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

MLA Handbook (7th Edition):

Raabe, Ines. “Salts of electrophilic cations and Lewis acid-base adducts with weakly coordinating anions: synthesis, characterization and quantum chemical calculations.” 2007. Web. 23 Oct 2019.

Vancouver:

Raabe I. Salts of electrophilic cations and Lewis acid-base adducts with weakly coordinating anions: synthesis, characterization and quantum chemical calculations. [Internet] [Thesis]. EPFL; 2007. [cited 2019 Oct 23]. Available from: http://infoscience.epfl.ch/record/103748.

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

Council of Science Editors:

Raabe I. Salts of electrophilic cations and Lewis acid-base adducts with weakly coordinating anions: synthesis, characterization and quantum chemical calculations. [Thesis]. EPFL; 2007. Available from: http://infoscience.epfl.ch/record/103748

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

3. Thiery, Guillaume, Jean, Gregoire. Synthèse et étude de l'activité catalytique de nouveaux complexes cationiques bien définis à base de gallium(I) et d'indium(I), évaluation de divers sels à l'anion faiblement coordinant en tant qu’abstracteurs d'halogénures. : Synthesis and study of the catalytic activity of new well-defined gallium(I) and indium(I)-based cationic complexes, evaluation of diverse weakly coordinating anion-containing salts as halide abstractors.

Degree: Docteur es, Chimie, 2016, Paris Saclay

Le premier projet de ce travail de doctorat a consisté à étudier l’activité catalytique de complexes à base de gallium(I), pour continuer à rechercher des alternatives aux catalyseurs à base de métaux nobles, plus communs, mais réputés coûteux et/ou toxiques. Le savoir-faire de l’équipe en catalyse par des complexes de gallium(III) a pu être réinvesti dans l’étude de ce bas degré d’oxydation du gallium, rarement étudié dans la littérature scientifique, dans l’espoir de détecter des réactivités et/ou sélectivités différentes d’avec des complexes de gallium(III). Ainsi, le complexe cationique bien défini de gallium(I) [Ga(PhF)2][Al(OC(CF3)3)4] a été employé dans une large gamme de réactions dans lesquelles les catalyseurs à base de gallium(III) avaient déjà fait leurs preuves, telles que l’hydroarylation d’arénynes, la réaction de Friedel-Crafts ou encore l’hydrogénation d’alcènes par transfert, pour laquelle une réactivité supérieure à celle des complexes usuellement utilisés au sein de l’équipe a été observée. Un analogue à base d’indium(I), [In(PhF)2][Al(OC(CF3)3)4], a également été étudié dans ces réactions, sans succès. En revanche, il s’est avéré efficace dans le cadre de réactions d’hydroamination d’aminoalcènes.En parallèle a été conduit un projet basé sur l’étude en tant qu’abstracteurs d’halogénures de complexes de divers métaux (argent, lithium, potassium, thallium(I)) comportant l’anion perfluoré, très volumineux et très faiblement coordinant [Al(OC(CF3)3)4]-. Dans le cadre de l’activation de pré-catalyseurs à base d’or(I), de gallium(III) ou d’indium(III) par abstraction d’halogénures, les sels d’argent sont les plus communément employés dans la littérature. Cependant, ces sels d’argents ne sont pas innocents en termes de réactivité. Par ailleurs, si les cations métalliques des sels employés en abstraction d’halogénures font l’objet d’un nombre raisonnable d’études dans la littérature, ce n’est pas autant le cas des anions qui leur sont associés : notre étude s’oriente selon ces deux problématiques. Il s’est avéré que les propriétés très faiblement coordinantes de l’anion [Al(OC(CF3)3)4]- ont mené à des réactivités et sélectivités différentes de celles obtenues avec l’emploi de sels plus usuels, AgSbF6 plus particulièrement, dans le cadre de réaction classiquement catalysées par l’or(I) ou le gallium(III) et déjà étudiées dans le premier projet de ce travail de thèse. Les complexes à base de gallium(I) et d’indium(I) impliqués dans le premier projet ont également été, succinctement, étudiés dans ce projet parallèle.

In the main project of this thesis work, the catalytic activity of gallium(I)-based complexes was explored. The aim was to keep on looking for alternatives to noble metals-based, more common catalysts, which have a reputation for being expensive and/or toxic. The know-how developed in the team on gallium(III)-based catalysis was reinvested into the study of this low oxidation degree of gallium, only scarcely studied in the literature. It was hoped to then detect different reactivity and/or…

Advisors/Committee Members: Gandon, Vincent (thesis director).

Subjects/Keywords: Gallium(I); Catalyse; Abstraction d'halogénures; Anion faiblement coordinant; Or(I); Indium(I); Gallium(I); Catalysis; Halide abstraction; Weakly Coordinating Anions; Gold(I); Indium(I)

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

APA (6th Edition):

Thiery, Guillaume, Jean, G. (2016). Synthèse et étude de l'activité catalytique de nouveaux complexes cationiques bien définis à base de gallium(I) et d'indium(I), évaluation de divers sels à l'anion faiblement coordinant en tant qu’abstracteurs d'halogénures. : Synthesis and study of the catalytic activity of new well-defined gallium(I) and indium(I)-based cationic complexes, evaluation of diverse weakly coordinating anion-containing salts as halide abstractors. (Doctoral Dissertation). Paris Saclay. Retrieved from http://www.theses.fr/2016SACLS414

Chicago Manual of Style (16th Edition):

Thiery, Guillaume, Jean, Gregoire. “Synthèse et étude de l'activité catalytique de nouveaux complexes cationiques bien définis à base de gallium(I) et d'indium(I), évaluation de divers sels à l'anion faiblement coordinant en tant qu’abstracteurs d'halogénures. : Synthesis and study of the catalytic activity of new well-defined gallium(I) and indium(I)-based cationic complexes, evaluation of diverse weakly coordinating anion-containing salts as halide abstractors.” 2016. Doctoral Dissertation, Paris Saclay. Accessed October 23, 2019. http://www.theses.fr/2016SACLS414.

MLA Handbook (7th Edition):

Thiery, Guillaume, Jean, Gregoire. “Synthèse et étude de l'activité catalytique de nouveaux complexes cationiques bien définis à base de gallium(I) et d'indium(I), évaluation de divers sels à l'anion faiblement coordinant en tant qu’abstracteurs d'halogénures. : Synthesis and study of the catalytic activity of new well-defined gallium(I) and indium(I)-based cationic complexes, evaluation of diverse weakly coordinating anion-containing salts as halide abstractors.” 2016. Web. 23 Oct 2019.

Vancouver:

Thiery, Guillaume, Jean G. Synthèse et étude de l'activité catalytique de nouveaux complexes cationiques bien définis à base de gallium(I) et d'indium(I), évaluation de divers sels à l'anion faiblement coordinant en tant qu’abstracteurs d'halogénures. : Synthesis and study of the catalytic activity of new well-defined gallium(I) and indium(I)-based cationic complexes, evaluation of diverse weakly coordinating anion-containing salts as halide abstractors. [Internet] [Doctoral dissertation]. Paris Saclay; 2016. [cited 2019 Oct 23]. Available from: http://www.theses.fr/2016SACLS414.

Council of Science Editors:

Thiery, Guillaume, Jean G. Synthèse et étude de l'activité catalytique de nouveaux complexes cationiques bien définis à base de gallium(I) et d'indium(I), évaluation de divers sels à l'anion faiblement coordinant en tant qu’abstracteurs d'halogénures. : Synthesis and study of the catalytic activity of new well-defined gallium(I) and indium(I)-based cationic complexes, evaluation of diverse weakly coordinating anion-containing salts as halide abstractors. [Doctoral Dissertation]. Paris Saclay; 2016. Available from: http://www.theses.fr/2016SACLS414

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