title: Dinuclear zinc hydride supported by an anionic bis(N-heterocyclic carbene) ligand.
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.
authors.forename: Arnab
authors.initials: A
authors.lastname: Rit
authors.forename: Thomas P
authors.initials: TP
authors.lastname: Spaniol
authors.forename: Jun
authors.initials: J
authors.lastname: Okuda
mesh_terms: D000838:Anions / Q000737:chemistry; D002245:Carbon Dioxide / Q000737:chemistry; D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry; D018360:Crystallography, X-Ray; D006571:Heterocyclic Compounds / Q000737:chemistry*; D008024:Ligands; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry; D008968:Molecular Conformation; D012821:Silanes / Q000737:chemistry; D015032:Zinc / Q000737:chemistry*
chemical_list: D000838:Anions; D056831:Coordination Complexes; D006571:Heterocyclic Compounds; D008024:Ligands; D012821:Silanes; D002245:Carbon Dioxide; C030011:carbene; D015032:Zinc; D008697:Methane