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

被引：38
|
作者：
Rit, Arnab [1 ]
Spaniol, Thomas P. [1 ]
Okuda, Jun [1 ]
机构：
[1] Rhein Westfal TH Aachen, Inst Anorgan Chem, D-52056 Aachen, Germany
来源：
CHEMISTRY-AN ASIAN JOURNAL | 2014年 / 9卷 / 02期
关键词：
carbon dioxide; homogeneous catalysis; hydrides; N-heterocyclic carbenes; zinc; N-HETEROCYCLIC CARBENE; RING-OPENING POLYMERIZATION; SINGLE-SITE CATALYSTS; ALTERNATING COPOLYMERIZATION; METHANOL SYNTHESIS; HYDROGEN-ATOMS; CARBON-DIOXIDE; ZN-H; COMPLEXES; BOND;
D O I：
10.1002/asia.201301268
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
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.
引用
收藏
页码：612 / 619
页数：8
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