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The isomerization and stereochemistry of some iridium hydride complexes /

Samples of fac and mer carbonyltrihydridotris(triphenylphosphine)iridium (III) were prepared and fully characterized by i.r., ('1)H and ('31)P n.m.r. spectroscopies. Isomeric interconversion at 25(DEGREES) C was demonstrated. The rates of isomerization and hydrogen loss from each isomer were independently measured. The similarity of these rates strongly supports a mechanism by which isomerization occurs through the oxidative addition and reductive elimination of molecular hydrogen. The results of deuterium labelling experiments were consistent with the isomerization mechanism, and further suggest that either trans-oxidative addition of hydrogen or intramolecular hydride interchange in the mer isomer may occur. Various partially deuterated analogues of the fac and mer isomer were formed by further reaction in solution and identified in the ('1)H n.m.r. spectrum. An unusual downfield isotope shift occurred when deuterium is in a position trans to hydride.

Identiferoai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.68525
Date January 1979
CreatorsYorke, William John.
PublisherMcGill University
Source SetsLibrary and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada
LanguageEnglish
Detected LanguageEnglish
TypeElectronic Thesis or Dissertation
Formatapplication/pdf
CoverageDoctor of Philosophy (Department of Chemistry)
RightsAll items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated.
Relationalephsysno: 000090104, proquestno: AAINK50594, Theses scanned by UMI/ProQuest.

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