The utility of a range of computational chemistry approaches for the prediction of the regioselectivity for hydroformylation processes and metal-ligand dissociation in a model organometallic system is considered to provide insight about computational strategies for use in catalysis. The hydroformylation reactions investigated are the Rh-catalyzed hydroformylation of terminal alkenes with triarylphosphine and chelating diphosphine ligands. As well, the dissociation of water from a Pt complex is considered to probe method effects on metal-ligand bonding. Several density functional theory (DFT) approaches and ab initio methods are considered. We demonstrate that the quality of the basis set selected for the calculations can play a vital role in the prediction of even the product distribution, and that correcting for basis set superposition error (BSSE) can be very important. As well, the study demonstrates a broad range of predictions achievable using a variety of DFT approaches, which is, as discussed, a manifestation of the challenges that are encountered for calculations involving transition metal molecular species, illustrating the critical need to gauge computational chemistry methods.

人们认为，一系列计算化学方法可用于预测有机金属模型系统中加氢甲酰化过程和金属-配体解离的区域选择性，以提供有关用于催化的计算策略的见解。所研究的加氢甲酰化反应是末端烯烃与三芳基膦和螯合二膦配体的Rh催化加氢甲酰化。同样，水从Pt络合物中解离也被认为是探测方法对金属-配体键合的影响。几种密度泛函理论（DFT）的方法和从头开始方法被考虑。我们证明，为计算选择的基集的质量在甚至产品分布的预测中都可以发挥至关重要的作用，而基集叠加误差（BSSE）的校正可能非常重要。同样，该研究表明，使用多种DFT方法可以实现广泛的预测，正如所讨论的，这是涉及过渡金属分子种类的计算所遇到的挑战的体现，说明了衡量计算化学方法的关键需求。