A rhenium-cyclohexane complex with preferential binding of axial C-H bonds: A probe into the relative ability of C-H, C-D, and C-C bonds as hyperconjugative electron donors?

被引：52
作者：
Lawes, Douglas J.
Darwish, Tamim A.
Clark, Timothy
Harper, Jason B.
Ball, Graham E.
机构：
[1] Univ Erlangen Nurnberg, Comp Chem Cent, D-91052 Erlangen, Germany
[2] Univ New S Wales, Sch Chem, Sydney, NSW 2052, Australia
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2006年 / 45卷 / 27期
关键词：
ab initio calculations; alkane ligands; C-H activation; hyperconjugation; NMR spectroscopy;
D O I：
10.1002/anie.200600313
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Which bonds bind better? According to NMR experiments with the alkane complex [CpRe(CO)2(cyclohexane)] at low temperatures, complexation with an axial proton is preferred over that through an equatorial one by about 1.5 kJ mol-1. Calculations support this order of binding energies. The preference is proposed to be due to stronger electron donation through hyperconjugation from a C-H bond than from a C-C bond. (Figure Presented) © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.
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收藏
页码：4486 / 4490
页数：5
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