A Germanium Isocyanide Complex Featuring (n → π*) Back-Bonding and Its Conversion to a Hydride/Cyanide Product via C-H Bond Activation under Mild Conditions

被引：51

作者：

Brown, Zachary D. ^{[1
]}

Vasko, Petra ^{[2
]}

Fettinger, James C. ^{[1
]}

Tuononen, Heikki M. ^{[2
]}

Power, Philip P. ^{[1
]}

机构：

[1] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA

[2] Univ Jyvaskyla, Dept Chem, FI-40014 Jyvaskyla, Finland

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 09期

基金：

芬兰科学院;

关键词：

REACTIVITY; MOLECULES; SILYLENE; GROUP-14; HYDROGEN; CRYSTAL; AR'; GE; SN;

D O I：

10.1021/ja211874u

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Reaction of the diarylgermylene Ge(Ar-Me6)(2) [Ar-Me6 = C6H3-2,6-(C6H2-2,4,6-(CH3)(3))(2)] with tert-butyl isocyanide gave the Lewis adduct species (Ar-Me6)(2)GeCNBut, in which the isocyanide ligand displays a decreased C-N stretching frequency consistent with an n --> pi* back-bonding interaction. Density functional theory confirmed that the HOMO is a Ge-C bonding combination between the lone pair of electrons on the germanium atom and the C-N pi* orbital of the isocyanide ligand. The complex undergoes facile C-H bond activation to produce a new diarylgermanium hydride/cyanide species and isobutene via heterolytic cleavage of the N-Bu-t bond.

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页码：4045 / 4048

页数：4

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