Synthesis, structure, and bonding of stable dialkylsilaketenimines

被引：54

作者：

Abe, T

Iwamoto, T ^{[1
]}

Kabuto, C

Kira, M

机构：

[1] Tohoku Univ, Grad Sch Sci, Res & Analyt Ctr Giant Mol, Aoba Ku, Sendai, Miyagi 9808578, Japan

[2] Tohoku Univ, Grad Sch Sci, Dept Chem, Sendai, Miyagi 9808578, Japan

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2006年 / 128卷 / 13期

关键词：

D O I：

10.1021/ja057917o

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Stable (N-aryl)- and (N-alkyl)dialkylsilaketenimines R2SiCNR′ [R = 1,1,4,4-tetrakis(trimethylsilyl)butane-1,4-diyl, R′ = 2,6-diisopropylphenyl (2a) and 1-adamantyl (2b)] were synthesized as blue and red crystals by the reactions of isolable dialkylsilylene 3 with 2,6-diisopropylphenyl isocyanide and 1-adamantyl isocyanide. X-ray single-crystal analysis disclosed that molecular structures of 2a and 2b were close to each other and were characterized to be allenic rather than zwitterionic or a silylene-isocyanide complex. The bonding characteristics of silaketenimines are found to be affected strongly by the substituents on silicon and nitrogen atoms. Remarkable red-shift of the π(Si=C) → π*(C=N) band of 2a [λmax/nm (ε) 647(156)] compared with that of 2b [465 nm (109)] is ascribed to lowering of the π*(C=N) orbital level due to significant interaction between π*(C=N) and π*(N-aryl) orbitals. Copyright © 2006 American Chemical Society.

引用

页码：4228 / 4229

页数：2

共 15 条

[1] Heavy allenes and cumulenes E=C=E′ and E=C=C=E′ (E = P, As, Si, Ge, Sn;: E′ = C, N, P, As, O, S) [J].