Two-state reactivity as a new concept in organometallic chemistry

被引:1067
作者
Schröder, D
Shaik, S
Schwarz, H
机构
[1] Tech Univ Berlin, Inst Organ Chem, D-10623 Berlin, Germany
[2] Hebrew Univ Jerusalem, Dept Organ Chem, IL-91904 Jerusalem, Israel
[3] Hebrew Univ Jerusalem, Lise Meitner Minerva Ctr Computat Quantum Chem, IL-91904 Jerusalem, Israel
关键词
D O I
10.1021/ar990028j
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
It is proposed that spin-crossing effects can dramatically affect reaction mechanisms, rate constants, branching ratios, and temperature behaviors of organometallic transformations. This phenomenon is termed two-state reactivity (TSR) and involves participation of spin inversion in the rate-determining step. While the present analysis is based on studies of transition metals under idealized conditions, several recent reports imply that TSR is by no means confined to the gas phase. In fact, participation of more than a single spin surface in the reaction pathways is proposed as a key feature in organometallic chemistry.
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收藏
页码:139 / 145
页数:7
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