Dinuclear Zinc Hydride Supported by an Anionic Bis(N‐Heterocyclic Carbene) Ligand

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.