Dinuclear Zinc Hydride Supported by an Anionic Bis(N‐Heterocyclic Carbene) Ligand |
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| Authors: | Dr. Arnab Rit Dr. Thomas P. Spaniol Prof. Dr. Jun Okuda |
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| Affiliation: | Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056 Aachen (Germany), Fax: (+49)?241‐80‐92644 |
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| Abstract: | 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 D2h 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 Zn? H 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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| Keywords: | carbon dioxide homogeneous catalysis hydrides N‐heterocyclic carbenes zinc |
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