The importance of conformational search: A test case on the catalytic cycle of the Suzuki–Miyaura cross-coupling

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)₂Pd] or [(P(i-Pr)₃)₂Pd]. The error bars associated with conformational diversity of the [(PPh₃)₂Pd] 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)₂Pd] catalyst is considered.