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C-C σ complexes of rhodium

被引：55
作者：
Brayshaw, Simon K.
Sceats, Emma L.
Green, Jennifer C. [1 ]
Weller, Andrew S.
机构：
[1] Univ Bath, Dept Chem, Bath BA2 7AY, Avon, England
[2] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England
来源：
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2007年 / 104卷 / 17期
基金：
英国工程与自然科学研究理事会;
关键词：
C-C activation; density functional theory;
D O I：
10.1073/pnas.0609824104
中图分类号：
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号：
07 ; 0710 ; 09 ;
摘要：
In this article, the complexes [Rh(lBinor-S')(PR3)][BAr4F] (R = Pr-i, Cy, C5H9) are described. A combination of x-ray crystallography, NMR spectroscopy, density functional theory, and "atoms in molecules" calculations unequivocally demonstrates that the complexes contain rare examples of metal C-C agostic interactions. Moreover, they are fluxional on the NMR time scale, undergoing rapid and reversible C-C activation. Kinetic data and calculations point to a bismetallacyclobutane, Rh(V), intermediate.
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页码：6921 / 6926
页数：6
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