Reactions of terminal alkynes with a bulky dialkylaluminum hydride:: Hydroalumination versus deprotonation

被引：37

作者：

Uhl, Werner ^{[1
]}

Er, Elif ^{[1
]}

Hepp, Alexander ^{[1
]}

Koesters, Jutta ^{[1
]}

Grunenberg, Joerg ^{[2
]}

机构：

[1] Univ Munster, Inst Anorgan & Analyt Chem, D-48149 Munster, Germany

[2] Tech Univ Carolo Wilhelmina Braunschweig, Inst Organ Chem, D-38106 Braunschweig, Germany

来源：

ORGANOMETALLICS | 2008年 / 27卷 / 14期

关键词：

D O I：

10.1021/om800190f

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

In recent investigations we found an easy access to dialkyl(alkynyl)aluminum compounds by the deprotonation of phenylethyne with di(tert-butyl)- and dimethylaluminum hydride with evolution of molecular hydrogen. In contrast, the reactions of the bulky hydride R2Al-H [R = CH(SiMe3)(2)] with different alkynes R-C C-H (R = CMe3, SiMe3, C6H5, H) yielded vinylic aluminum compounds, R2Al-CH=CH-R', by hydroalumination. Due to the effective steric shielding of the bulky alkyl substituents, the products were monomeric even in the solid state, with the alkenyl groups bonded to coordinatively unsaturated, tricoordinated aluminum atoms. Quantum-chemical calculations verified that there was no interaction between the pi-electrons of the C=C bond and the vacant p-orbital at the coordinatively unsaturated aluminum atoms.

引用

页码：3346 / 3351

页数：6

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