The importance of conformational search: a test case on the catalytic cycle of the Suzuki-Miyaura cross-coupling
The importance of conformational search: a test case on the catalytic cycle of the Suzuki-Miyaura cross-coupling
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DOI：
10.1007/s00214-010-0823-6
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发表时间：
2011-03-01
影响因子：
1.7
通讯作者：
Lledos, Agusti
中科院分区：
文献类型：
--
作者：
Besora, Maria;Braga, Ataualpa A. C.;Lledos, Agusti
即使涉及相对较大的系统，构象多样性也是过渡金属配合物计算研究中经常被忽视的一个方面。通过分析 [(PPh3)(2)Pd] 或 [(P(i-Pr)(3))(2)Pd] 催化的 CH2=CHBr 和 CH2=CHB(OH)(2) 之间的 Suzuki-Miyaura 交叉偶联的计算研究中构象异构体选择错误可能导致的错误，说明了构象搜索的重要性。与 [(PPh3)(2)Pd] 催化剂构象多样性相关的误差线范围在 0.3 至 6.7 kcal/mol 之间，当考虑更灵活的 [(P(i-Pr)(3))(2)Pd] 催化剂时，该值增至 11.4 kcal/mol。
Conformational diversity is an often neglected aspect in computational studies of transition metal complexes, even when relatively large systems are involved. The importance of conformational searches is illustrated through the analysis of the errors that could be caused by a wrong choice of conformers in the computational study of the Suzuki-Miyaura cross-coupling between CH2=CHBr and CH2=CHB(OH)(2) catalyzed by [(PPh3)(2)Pd] or [(P(i-Pr)(3))(2)Pd]. The error bars associated with conformational diversity of the [(PPh3)(2)Pd] catalyst range between 0.3 and 6.7 kcal/mol, the values growing up to 11.4 kcal/mol when the more flexible [(P(i-Pr)(3))(2)Pd] catalyst is considered.