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Dinuclear Zinc Hydride Supported by an Anionic Bis(N‐Heterocyclic Carbene) Ligand
Author(s) -
Rit Arnab,
Spaniol Thomas P.,
Okuda Jun
Publication year - 2014
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201301268
Subject(s) - carbene , chemistry , hydride , ligand (biochemistry) , zinc , medicinal chemistry , polymer chemistry , combinatorial chemistry , organic chemistry , catalysis , hydrogen , receptor , biochemistry
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 PhSiH 3 gave the phenylsilyl compound 3 . The zinc hydride 4 was obtained by the reaction of 2 with LiAlH 4 or Ph 3 SiOH followed by treatment with PhSiH 3 . X‐ray diffraction studies show that compounds 2 , 3 , and 4 all have a similar dimeric structure with D 2 h 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 Ph 2 CO gave the diphenylmethoxy compound 6 . Hydride 4 shows catalytic activity in the hydrosilylation of 1,1‐diphenylethylene and methanolysis of silanes.