Facile Conversion of Bis-Silylene to Cyclic Silylene Isomers: Unexpected C-N and C-H Bond Cleavage

被引：8
作者：
Wang, Yuzhong
Hickox, Hunter P.
Xie, Yaoming
Wei, Pingrong
Schaefer, Henry F., III
Robinson, Gregory H. [1 ]
机构：
[1] Univ Georgia, Dept Chem, Athens, GA 30602 USA
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 45期
基金：
美国国家科学基金会;
关键词：
GROUP; 14; ELEMENT; HETEROCYCLIC CARBENES; RING-EXPANSION; STABLE SILYLENE; ACTIVATION; 2-COORDINATE; REACTIVITY; COMPLEXES; SILICON; CHLOROSILYLENE;
D O I：
10.1021/jacs.7b10325
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Reaction of thiolate 1 with carbene-stabilized diiodo-bis-silylene (2) (in a 2:1 ratio) in THF unexpectedly gives both the first five-membered, sulfur containing, zwitterionic silylene ring (3) via insertion of the "Si-2(I)" unit of 2 into the olefinic C-H bond of the imidazole ring of 1 and four-membered cyclic silylene (4) via insertion of a silicon(I) atom of 2 into the C-phenyl-N bond of the carbene ligand. The parallel reaction in toluene only gives 3 as the major product. The nature of the bonding in isomeric 3 and 4 was probed by experimental and theoretical methods.
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收藏
页码：16109 / 16112
页数：4
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