P-P and P-Sb coordination chemistry

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dc.contributor.authorChitnis, Saurabh Sunil
dc.contributor.supervisorBurford, Neil
dc.date.accessioned2015-04-21T21:33:32Z
dc.date.available2016-04-17T11:22:06Z
dc.date.copyright2015en_US
dc.date.issued2015-04-21
dc.degree.departmentDepartment of Chemistry
dc.degree.levelDoctor of Philosophy Ph.D.en_US
dc.description.abstractThe coordination chemistry of compounds featuring P-P and P—Sb bonds has been investigated to define the fundamental features of bonding in these systems. New reaction methodologies to form P—P bonds have been evolved based on careful consideration of bond strengths in the gas and condensed phase. Insights revealed from systematic studies of molecular structures have been used to augment and expand the scope of existing models for structural prediction (e.g. VSEPR theory). Unique classes of catena-antimony compounds have been discovered, illustrating a remarkable structural and electronic diversity for this heavy p-block metal. Detailed mechanistic examinations have revealed a previously unrecognized mode of ligand activation for phosphine complexes of very electrophilic acceptors. Stable sources of the hitherto unisolated and highly reactive tris-triflate reagents, E(OTf)3 (E = P, As, Sb, Bi), have been prepared and their coordination chemistry as Lewis acids and oxidizing agents has been mapped. Collectively, the findings described here span a range of coordination chemistry paradigms for p-block elements that may be broadly applicable across the periodic table. A robust plan has been proposed for applying these insights towards the preparation of fundamentally interesting molecular frameworks and towards new strategies for small molecule activation.en_US
dc.description.proquestcode0488en_US
dc.description.proquestcode0485en_US
dc.description.proquestemailsschitnis@gmail.comen_US
dc.description.scholarlevelGraduateen_US
dc.identifier.bibliographicCitationS. S. Chitnis, N. Burford, J. J. Weigand, R. McDonald, "Multi-electron Reductive Catenation of Phosphine-Antimony Complexes", Angew. Chem. Int. Ed., Submitted.en_US
dc.identifier.bibliographicCitationA. P. M. Robertson, S. S. Chitnis, H. A. Jenkins, R. McDonald, M. J. Ferguson, and N. Burford, “Establishing the Coordination Chemistry of Antimony(V) Cations: Systematic Assessment of Ph4Sb(OTf) and Ph3Sb(OTf)2 as Lewis Acceptors”, Chem. Eur. J., In press.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, A. P. M. Robertson, N. Burford, J. J. Weigand, and R. Fischer, 'Synthesis and Reactivity of Cyclo-tetra(stibinophosphonium) Tetracations: Redox and Coordination Chemistry of Phosphine-Antimony Complexes', Chem. Sci., 2015, 6, 2559-2574.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, and N. Burford, 'Phosphine complexes of lone-pair bearing acceptors', Dalton Trans., 2015, 44, 17-29.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, M. Whalen, and N. Burford, 'Influence of Charge and Coordination Number on Bond Dissociation Energies, Distances and Vibrational Frequencies for the Phosphorus-Phosphorus Bond', J. Am. Chem. Soc., 2014, 136, 12498-12506.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, N. Burford, R. McDonald, and M. J. Ferguson, 'Prototypical Phosphine Complexes of Antimony(III)', Inorg. Chem., 2014, 53, 5359-5372.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, N. Burford, A. Decken, and M. J. Ferguson, 'Coordination Complexes of Bismuth Triflates with THF and Diphosphine Ligands', Inorg. Chem., 2013, 52, 7242-7248.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, Y. Carpenter, N. Burford, R. McDonald and M. Ferguson, 'Assembly of a cyclo -tetrastibinotetraphosphonium Tetracation by Reductive Elimination', Angew. Chem. Int. Ed., 2013, 52, 4863-4866.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, N. Burford, and M. J. Ferguson, '2,2-Bipyridine Complexes of Antimony: Sequential Fluoride Ion Abstraction from SbF3 by Exploiting the Fluoride Ion Affinity of Me3Si+', Angew. Chem. Int. Ed., 2013, 52, 2042-2045.en_US
dc.identifier.bibliographicCitationE. MacDonald, L. Doyle, S. S. Chitnis, U. Werner-Zwanziger, N. Burford, and A. Decken, 'Me3P Complexes of P-block Lewis Acids SnCl4, [SnCl3]1+, and [SnCl2]2+', Chem. Commun., 2012, 48, 7922-7924.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, E. MacDonald, N. Burford, U. Werner-Zwanziger, and R. McDonald, 'P-P Menschutkin Preparation of Prototypical Phosphinophosphonium Salts', Chem. Commun., 2012, 48, 7359-7361.en_US
dc.identifier.bibliographicCitationS. S. Chitnis, B. Peters, E. Conrad, N. Burford, R. McDonald, and M. J. Ferguson, 'Structural Diversity for Phosphine Complexes of Stibenium and Stibinidenium Cations', Chem. Commun., 2011, 47, 12331-12333.en_US
dc.identifier.urihttp://hdl.handle.net/1828/5981
dc.languageEnglisheng
dc.language.isoenen_US
dc.rightsAvailable to the World Wide Weben_US
dc.rights.tempAvailable to the World Wide Weben_US
dc.rights.tempAttribution-NonCommercial-NoDerivs 2.5 Canada*
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/2.5/ca/*
dc.subjectchemistryen_US
dc.subjectinorganic chemistryen_US
dc.subjectcrystallographyen_US
dc.subjectcoordination chemistryen_US
dc.subjectmain group chemistryen_US
dc.subjectsynthesisen_US
dc.subjectphosphorusen_US
dc.subjectantimonyen_US
dc.subjectcatenationen_US
dc.subjectLewis acidsen_US
dc.titleP-P and P-Sb coordination chemistryen_US
dc.typeThesisen_US

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