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DC Field | Value | Language |
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dc.contributor.advisor | Maitlis, P.M. | en_US |
dc.contributor.author | Lee, Hing-Biu | en_US |
dc.date.accessioned | 2014-06-18T16:43:09Z | - |
dc.date.available | 2014-06-18T16:43:09Z | - |
dc.date.created | 2010-12-21 | en_US |
dc.date.issued | 1974-05 | en_US |
dc.identifier.other | opendissertations/3718 | en_US |
dc.identifier.other | 4735 | en_US |
dc.identifier.other | 1703748 | en_US |
dc.identifier.uri | http://hdl.handle.net/11375/8518 | - |
dc.description.abstract | <p>Reactions of the complexes [C₅Me₅MCl₂]₂ (M=Rh and Ir) with alcoholic base gave the bridged hydrides (C₅Me₅M)₂HCl₃.</p> <p>The hydrides reacted readily at room temperature with cyclic and acyclic diolefins to give π-allylic complexes, the cyn- isomers being the ones obtained when a choice was available. When both terminal and internal double bonds were present, addition of M-H occurred preferentially to the terminal double bond.</p> <p>The allylic complexes showed varying degrees of stability towards reductive elimination (by lossof HCl) and the formation of 1,3-diene complexes. Allyis with only syn-substituents were stable towards diene complex formation. Those with an additional C-2 methyl substituent were less stable and the diene complexes could be obtained under moderately drastic conditions, presumably via G-allyl intermediates. Allyls with an anti-methyl or -methylene substituent underwent reductive elimination of HCI to give diene complexes spontaneously and these reactions were accelerated by the presence of triethylamine.</p> <p>Kinetic studies on these hydride-diene reactions indicated that the reactions were first-order with respect to the hydride and independent of the nature and concentration of the diene. Except for 2,5-dimethyl-2,4-hexadiene, all dienes studied reacted at the same rate with the same hydride. The deuterides (C₅Me₅M)₂DCl₃ did not show any significant kinetic isotope effect. These results suggested that the rate-determining step of these hydride-diene reactions was the cleaving of the chloride bridge to create a vacant site. Mechanisms for the formation and decompositions of the allyls are proposed.</p> <p>Reactions of [C₅Me₅MCl₂]₂ with dibenzylideneacetone, allyl cyanide and some β-diketones are described.</p> | en_US |
dc.subject | Chemistry | en_US |
dc.subject | Chemistry | en_US |
dc.title | Reactions of Some Rhodium and lridium Hydrides | en_US |
dc.type | thesis | en_US |
dc.contributor.department | Chemistry | en_US |
dc.description.degree | Doctor of Philosophy (PhD) | en_US |
Appears in Collections: | Open Access Dissertations and Theses |
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fulltext.pdf | 3.8 MB | Adobe PDF | View/Open |
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