期刊
CHEMISTRY-AN ASIAN JOURNAL
卷 9, 期 2, 页码 612-619出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/asia.201301268
关键词
carbon dioxide; homogeneous catalysis; hydrides; N-heterocyclic carbenes; zinc
资金
- Cluster of Excellence RWTH Aachen Tailor-Made Fuels from Biomass
- Deutsche Forschungsgemeinschaft through the International Research Training Group Selectivity in Chemo- and Biocatalysis
Methylene-linked bis(N,N-di-tert-butylimidazol-2-ylidene) 1 reacted with diethylzinc to give dinuclear zinc ethyl compound 2, which contains a formally anionic bis(carbene) ligand as a result of deprotonation of the methylene bridge. The reaction of 2 with PhSiH3 gave the phenylsilyl compound 3. The zinc hydride 4 was obtained by the reaction of 2 with LiAlH4 or Ph3SiOH followed by treatment with PhSiH3. X-ray diffraction studies show that compounds 2, 3, and 4 all have a similar dimeric structure with D-2h symmetry. The reaction of hydride 4 with carbon dioxide and N,N-diisopropylcarbodiimide gave formato (5) and formamidinato (7) derivatives as a result of the insertion of the heterocumulene into both ZnH bonds. Reaction with Ph2CO gave the diphenylmethoxy compound 6. Hydride 4 shows catalytic activity in the hydrosilylation of 1,1-diphenylethylene and methanolysis of silanes.
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