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UBC Theses and Dissertations

Addition-transfer reactions of zirconium alkyne complexes Mylvaganam, Murugesapillai


A unique type of reaction, namely the addition-transfer process, has been developed. This reaction transforms the zirconium alkyne complexes, Cp2Zr(η²-alkyne)(PMe₃), to 2-diphenylphosphino and 2-trimethylstannyl alkenyl zirconium compounds by reaction with Ph₂PCI and Me₃SnCl respectively. In the former process, the Ph₂P group is found to be cis to the Cp₂ZrCl group whereas, in the latter case, the Me₃Sn and the Cp₂ZrCl moieties are trans to one another. This reaction was also used to synthesize dienyl zirconium compounds having Ph₂P substitutions on the diene. Preliminary mechanistic proposals suggest that the Ph₂PCI is reacting via a four-centre pathway involving the P-Cl bond and one of the Zr-C bonds of the zirconium alkyne complex; whereas Me₃SnCl reacts via a transition state similar to a π-complex.

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