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Title Investigations into the Reactivity and Structure of Phosphinophosphonium Cations and Related Species
Publication Date
Degree PhD
Discipline/Department Department of Chemistry
Degree Level doctoral
University/Publisher Dalhousie University
Abstract Carbon and phosphorus have often been compared owing to their diagonal relationship on the periodic table. However, relative to carbon, there remains an enormous breadth of polyphosphorus chemistry that is unexplored, particularly in the area of cationic phosphorus. A key step in the systematic and rational development of larger catenated organo-polyphosphorus cations is a fundamental understanding of the reactivity of small cationic building blocks. The smallest catenated framework in this context is the phosphinophosphonium monocation [R3P-PR2]+ (or phosphine-stabilized phosphenium cation), which can be prepared with a variety of functional groups at either phosphorus centre. This dissertation explores the diverse reactivity of chloro-substituted phosphinophosphonium cations, with a particular focus on reductive coupling as a synthetic route to novel catena-phosphorus systems. The resulting cationic frameworks are comprehensively described in terms of their diasteroisomerism, solution dynamics, and solid-state structural features. Additionally, fundamental electrochemical investigations of these diphosphorus cations are outlined as a tool for understanding and quantifying the reactivity of phosphenium cations. Finally, extension of reductive coupling methodology to the first chlorostibinophosphonium cations presents a promising outlook towards the catenation of the heavier pnictogen cations.
Subjects/Keywords phosphorus; antimony; cations; inorganic chemistry; synthetic chemistry; electrochemistry; main group chemistry
Contributors David J. H. Emslie (external-examiner); D. Jean Burnell (graduate-coordinator); Russell J. Boyd (thesis-reader); Alison Thompson (thesis-reader); Mark N. Obrovac (thesis-reader); Neil Burford (thesis-supervisor); Not Applicable (ethics-approval); Not Applicable (manuscripts); Not Applicable (copyright-release)
Language en
Country of Publication ca
Format application/pdf
Record ID handle:10222/13165
Other Identifiers TC-NSHD-13165
Repository canada
Date Indexed 2017-01-03
Grantor Dalhousie University

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…Investigations into the Reactivity and Structure of Phosphinophosphonium Cations and Related Species by Yuen-ying S. Carpenter Submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy at Dalhousie University

…Halifax, Nova Scotia December 2010 Copyright by Yuen-ying S. Carpenter, 2010 DALHOUSIE UNIVERSITY DEPARTMENT OF CHEMISTRY The undersigned hereby certify that they have read and recommend to the Faculty of Graduate Studies for acceptance a thesis…

…_________________________________ ii DALHOUSIE UNIVERSITY DATE: December 7, 2010 AUTHOR: Yuen-ying S. Carpenter TITLE: Investigations into the Reactivity and Structure of Phosphinophosphonium Cations and Related Species DEPARTMENT OR SCHOOL: DEGREE: PhD Department of…

…Chemistry CONVOCATION: May YEAR: 2011 Permission is herewith granted to Dalhousie University to circulate and to have copied for non-commercial purposes, at its discretion, the above title upon the request of individuals or institutions. I understand that…