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Addition-transfer reactions of zirconium alkyne complexes Mylvaganam, Murugesapillai
Abstract
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.
Item Metadata
| Title |
Addition-transfer reactions of zirconium alkyne complexes
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| Creator | |
| Publisher |
University of British Columbia
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| Date Issued |
1989
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| Description |
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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| Genre | |
| Type | |
| Language |
eng
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| Date Available |
2010-08-22
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| Provider |
Vancouver : University of British Columbia Library
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| Rights |
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.
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| DOI |
10.14288/1.0059527
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| URI | |
| Degree (Theses) | |
| Program (Theses) | |
| Affiliation | |
| Degree Grantor |
University of British Columbia
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| Campus | |
| Scholarly Level |
Graduate
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| Aggregated Source Repository |
DSpace
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Rights
For non-commercial purposes only, such as research, private study and education. Additional conditions apply, see Terms of Use https://open.library.ubc.ca/terms_of_use.