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dc.contributor.authorWechsler, Dominik.en_US
dc.date.accessioned2014-10-21T12:33:52Z
dc.date.available2014-10-21T12:33:52Z
dc.date.issued2007en_US
dc.identifier.otherAAINR31506en_US
dc.identifier.urihttp://hdl.handle.net/10222/54969
dc.descriptionHomogeneous transition metal catalysts are commonly made up of transition metals bound to one or more ligands, where the electronic and steric contributions of the ligands can have a significant impact upon the reactivity and selectivity of the catalyst in mediating various substrate transformations, such as the activation of E-H bonds (E = main group element) in small molecule substrates. The development of new catalyst structural motifs through the design of new ancillary ligands is a persistent challenge in organometallic chemistry.en_US
dc.descriptionIn this thesis, the development of new ancillary ligands derived from a P,N substituted indene backbone (1-3a) has been discussed. 1-P(S)iPr2-2-NMe2-indene 2-3a was prepared via a one-step synthetic pathway from 1-3a and has been shown to support neutral and cationic Rh(I) and Ir(I) fragments, in a kappa2-C,S and kappa2-N,S fashion (respectively). The neutral kappa2-C,S Rh complex 2-7a (the first complex featuring a Rh-C-P-S ring system, as well as the first eta1-indenylrhodium species to be crystallographically characterized) has shown similar catalytic activity and regioselectivity to that of Wilkinson's catalyst 1-1 under some conditions. In the presence of water, clean conversion of complexes 2-6a,b to the (COD)M(kappa2-P(S),O) complexes 2-10a,b has been demonstrated; 2-10a,b have shown similar catalytic activity and regioselectivity to those observed with 2-7a for the addition of triethylsilane to styrene. The incorporation of chirality into the P,N binding site of ligand 1-3a afforded ligand 2-11b and the metal coordination chemistry and catalytic activity of 2-11b is unlike that observed with 1-3a.en_US
dc.descriptionThe ability of the P,N ligand (1-3a) to support two metal fragments (eta5-MLn and kappa2- P,N) has been demonstrated confirming its ambidentate function. The catalytic ability of these racemic bimetallic complexes 3-3a-c has also been explored in the hydroboration of styrene with pinacolborane. The results of this preliminary catalytic survey revealed that structural changes to the eta5-coordinated metal fragment (MLn = Mn(CO) 3 3-3a, RuCp* 3-3b or FeCp* 3-3c) may provide a systematic way to modify and influence the steric and electronic properties of the kappa2-P,N-ligated metal fragment in these complexes.en_US
dc.descriptionThe development of a new chiral P,N ligand 4-1 derived from 7-azaindole was also discussed. Ligand 4-1 was prepared in an easy and modular manner and showed divergent metal coordination chemistry with transition metals such as Rh, Ir and Pd. In certain catalytic asymmetric transformations (hydrogenation and allylic alkylation reactions) some of these metal complexes have demonstrated good catalytic activity and enantioselectivity.en_US
dc.descriptionThesis (Ph.D.)--Dalhousie University (Canada), 2007.en_US
dc.languageengen_US
dc.publisherDalhousie Universityen_US
dc.publisheren_US
dc.subjectChemistry, Inorganic.en_US
dc.titleSynthesis and reactivity of late metal complexes featuring new heterobidentate ancillary ligands.en_US
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dc.contributor.degreePh.D.en_US
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