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.
| Identifer | oai:union.ndltd.org:LACETR/oai:collectionscanada.gc.ca:QMM.68525 |
| Date | January 1979 |
| Creators | Yorke, William John. |
| Publisher | McGill University |
| Source Sets | Library and Archives Canada ETDs Repository / Centre d'archives des thèses électroniques de Bibliothèque et Archives Canada |
| Language | English |
| Detected Language | English |
| Type | Electronic Thesis or Dissertation |
| Format | application/pdf |
| Coverage | Doctor of Philosophy (Department of Chemistry) |
| Rights | All items in eScholarship@McGill are protected by copyright with all rights reserved unless otherwise indicated. |
| Relation | alephsysno: 000090104, proquestno: AAINK50594, Theses scanned by UMI/ProQuest. |
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