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The oxidation of olefins promoted by transition metal complexesJohn, Robert Alun January 1981 (has links)
The oxidation of olefins by transition metal complexes leading to epoxide or ketonic products has been reviewed, with an emphasis on non-free radical processes. The formation of cycloadducts by reaction of <u>bis</u> (triphenylphosphine )- platinum(O)dioxygen with the α,β-unsaturated carbonyl compounds <u>trans</u> but-2-enal, propenal, cyclohex-2-en-1-one, <u>exo</u> 2-methvlenecyclohexan-1-one and 3-phenylprop- 2-enal was investigated by H- and <sup>31</sup>P- nuclear magnetic resonance (n.m.r.). The cycloadducts derived from <u>trans</u> but-2-enal and propenal were thermally unstable in solution and further reacted to form stable, isolable complexes. The mechanism by which the cycloadduct <u>cis</u> [4-<u>trans</u>(prop-2-enyl )-1,1-bis( triphenyl - phosphine)platina-2,3» 5-trioxacyclopentane] , I , was transformed into <u>cis</u> [<u>trans</u>- (5-formyl-4-methyl)-1,1-bis(triphenylphosphine )platina-2 t 3-dioxacyclopentane] , II , was investigated by H- and H-n.m.r. utilising <u>trans</u> 4-[<sup>2</sup>H<sub>3</sub>]but-2-enal. A mechanism which involved both exchange of free <u>trans</u> but-2-enal with I and reaction to give II was proposed; a computer model, based upon numerical integration of the alternative rate equations was in good agreement with this proposition. The chemical reactivity of II with a variety of reagents was explored. In particular, the reaction of II with trifluoroacetic acid gave <u>trans</u> 2-formyl- 3-methyloxirane in high yield and stereoselectivity. The dynamic behaviour of <u>cis</u>[<i>bis</u>(triphenylphosphine)(2<sub>3</sub>,3'-m)(<u>trans</u> - but-2-enal )platinum(0)] was observed by variable temperature P-n.m.r. and explained by the interconversion of carbonyl rotamers. The preparation of iridium(I) olefin and peroxo complexes has been described Chloro<u>bis</u> triphenylphosphine) (1,2-m) (ethene )dioxygen iridium( I) , III , and related complexes were found to oxidise terminal olefins to their methyl ketones stoichiometrically, by a non-free radical process. The mechanism has been discussed.
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Studies in organo-transition metal chemistry / by Michael John LiddellLiddell, Michael John January 1989 (has links)
Typescript (Photocopy) / Includes bibliographical references / xix, 290 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--Dept. of Physical and Inorganic Chemistry, University of Adelaide, 1989
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Comparative X-ray Structure Analyses of Multidentate Transition Metal ComplexesFlood, Kelly-Jayne January 2006 (has links)
The biological significance of macrocyclic complexes has been recognized since they were first synthesized by Neil Curtis. They have the potential to play a critical role in mimicking metalloprotein active sites. Nine Curtis macrocyclic complexes have been studied using X-ray crystallographic techniques. Their structures have been solved and comparisons of the results have been made. Biological importance is also true of the macrocyclic counterpart; side-off and end-off compartmental ligands. In some circumstances these types of ligands are more appropriate because they have extra flexibility due to their pendant arms not being fixed in place by another head-unit, like a traditional macrocycle. The synthesis of a proposed compartmental ligand; 2,2-(N,Nʼ-bis(benzimidazole-2-ylmethyl)methylamine-5,5ʼ-di-tert-butyl-3,3ʼmethanediyl-dibenzyl alcohol (Ligand 1(L1)), has been proposed and outlined. The pendant arms: bis(benzimidazole-2-ylmethyl)amine (BBIM), were successfully synthesized and characterized with 1H NMR, IR and X-ray crystallography. The head-unit: 5,5ʼ-Di-tert-butyl-2,2ʼ-dihydroxy-3,3ʼ-methanediyl-dibenzene methanol (DHTMBA), of L1 was synthesized and characterized using 1H NMR, IR and mass spectrometry. A similar head-unit; 5,5ʼ-Di-methyl-2,2ʼ-dihydroxy-3,3ʼ-methanediyl-dibenzene methanol (DHMMBA), was synthesized in an effort to shorten the synthetic time of the head-unit. This was consequently converted to the chlorine analogue; 3,3ʼ-Bis(chloromethyl)-5,5ʼ-dimethyl-2,2ʼ-methane-diyldiphenol (Cl-DHMMB), and characterized with 1H NMR, IR and X-ray crystallography. Efforts were made to synthesize Ligand 1, but due to synthetic difficulties and time restraints this proved unsuccessful. Suggestions have been made to develop this synthesis.
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Effects of copper-ligand and copper-copper interactions on excited state properties of luminescent copper (I) complexes : structural and photophysical studies /Mao, Zhong. January 2003 (has links)
Thesis (Ph. D.)--University of Hong Kong, 2007.
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The sequential insertion of carbon monoxide and imines into nickel-carbon [sigma]-bonds and kinetic analysis of imine insertion into palladium-acyl [sigma]-bondsStafford, Carolyne. January 1900 (has links)
Thesis (M.Sc.). / Written for the Dept. of Chemistry. Title from title page of PDF (viewed 2008/01/16). Includes bibliographical references.
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Dicationic dihydrogen complexes of osmium and ruthenium /Luther, Thomas Alan, January 1997 (has links)
Thesis (Ph. D.)--University of Washington, 1997. / Vita. Includes bibliographical references (leaves [135]-142).
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Transition metal complexes of protoporphyrin IX formed by reaction with metals on claysKlube, John Arthur, January 1976 (has links)
Thesis (M.S.)--South Dakota School of Mines and Technology, Rapid City, 1976. / Vita. Includes abstract. Includes bibliographical references (leaf 29). Also issued in print.
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Design and syntheses of luminescent rhenium(I) diimine alkynyl complexes with hole-transporting and/or electron-transporting moieties and their use as potential triplet emittersChung, Wai-kin. January 2009 (has links)
Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 304-323). Also available in print.
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Design, synthesis, and photophysical and electrochemical studies of redox-active macrocyclic dinuclear transition metal complexes as potential molecular switchesKong, Jianfei. January 2009 (has links)
Thesis (Ph. D.)--University of Hong Kong, 2009. / Includes bibliographical references (leaves 214-229). Also available in print.
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From dihydrogen complexes to polyhydrides /Pons, Vincent, January 2004 (has links)
Thesis (Ph. D.)--University of Washington, 2004. / Vita. Includes bibliographical references (leaves 152-158).
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