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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Accurate computed spin-state energetics for Co(III) complexes: implications for modelling homogeneous catalysis
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Accurate computed spin-state energetics for Co(III) complexes: implications for modelling homogeneous catalysis

机译：CO（III）复合物的准确计算的旋转状态能量学：对均匀催化建模的影响

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摘要

Co(III) complexes are increasingly prevalent in homogeneous catalysis. Catalytic cycles involve multiple intermediates, many of which will feature unsaturated metal centres. This raises the possibility of multistate character along reaction pathways and so requires an accurate approach to calculating spin-state energetics. Here we report an assessment of the performance of DLPNO-CCSD(T) (domain-based local pair natural orbital approximation to coupled cluster theory) against experimental Co-1 to Co-3 spin splitting energies for a series of pseudo-octahedral Co(III) complexes. The alternative NEVPT2 (strongly-contracted n-electron valence perturbation theory) and a range of density functionals are also assessed. DLPNO-CCSD(T) is identified as a highly promising method, with mean absolute deviations (MADs) as small as 1.3 kcal mol(-1) when Kohn-Sham reference orbitals are used. DLPNO-CCSD(T) out-performs NEVPT2 for which a MAD of 3.5 kcal mol(-)(1 )can be achieved when a (10,12) active space is employed. Of the nine DFT methods investigated TPSS is the leading functional, with a MAD of 1.9 kcal mol(-1). Our results show how DLPNO-CCSD(T) can provide accurate spin state energetics for Co(III) species in particular and first row transition metal systems in general. DLPNO-CCSD(T) is therefore a promising method for applications in the burgeoning field of homogeneous catalysis based on Co(III) species.
机译：CO（III）复合物在均匀催化中越来越普遍。催化循环涉及多种中间体，其中许多将具有不饱和金属中心。这提高了沿反应途径的多态特征的可能性，因此需要准确的方法来计算旋转状态能量。在这里，我们报告了对DLPNO-CCSD（T）（基于结构域的本地对自然轨道近似与耦合群集理论）的性能进行评估，针对实验CO-1至CO-3旋转分裂能量，用于一系列伪八面体CO（ III）复合物。还评估替代的Nevpt2（强缩合的N型电子价扰动理论）和一系列密度官能。 DLPNO-CCSD（T）被识别为高度有希望的方法，当使用Kohn-Sham参考轨道时，平均绝对偏差（MAD）小于1.3千卡摩尔（-1）。 DLPNO-CCSD（T）OUT-DENT-DENVPT2，当使用（10,12）的有效空间时，可以实现3.5千卡MOL（ - ）（1）的MAD。在九种DFT方法中调查TPS是主要的功能，疯狂的1.9千卡摩尔（-1）。我们的结果表明DLPNO-CCSD（T）如何为特定的CO（III）种类提供精确的旋转状态能量，以及一般的第一行过渡金属系统。因此，DLPNO-CCSD（T）是基于CO（III）物种的均质催化的新兴领域的应用方法。

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