Castro Abril C, Fliegl Heike, Cascella Michele, Helgaker Trygve, Repisky Michal, Komorovsky Stanislav, Medrano María Ángeles, Quiroga Adoración G, Swart Marcel
Institut de Química Computacional i Catàlisi (IQCC), Departament de Química, Universitat de Girona, Campus Montilivi, 17003, Girona, Spain.
Dalton Trans. 2019 Jun 11;48(23):8076-8083. doi: 10.1039/c9dt00570f.
We report a combined experimental-theoretical study on the 31P NMR chemical shift for a number of trans-platinum(ii) complexes. Validity and reliability of the 31P NMR chemical shift calculations are examined by comparing with the experimental data. A successful computational protocol for the accurate prediction of the 31P NMR chemical shifts was established for trans-[PtCl2(dma)PPh3] (dma = dimethylamine) complexes. The reliability of the computed values is shown to be critically dependent on the level of relativistic effects (two-component vs. four component), choice of density functionals, dynamical averaging, and solvation effects. Snapshots obtained from ab initio molecular dynamics simulations were used to identify those solvent molecules which show the largest interactions with the platinum complex, through inspection by using the non-covalent interaction program. We observe satisfactory accuracy from the full four-component matrix Dirac-Kohn-Sham method (mDKS) based on the Dirac-Coulomb Hamiltonian, in conjunction with the KT2 density functional, and dynamical averaging with explicit solvent molecules.
我们报告了一项关于多种反式铂（II）配合物的³¹P NMR化学位移的实验与理论相结合的研究。通过与实验数据比较，检验了³¹P NMR化学位移计算的有效性和可靠性。针对反式-[PtCl₂(dma)PPh₃]（dma = 二甲胺）配合物，建立了一种准确预测³¹P NMR化学位移的成功计算方法。计算值的可靠性显示出严重依赖于相对论效应水平（二分量与四分量）、密度泛函的选择、动态平均以及溶剂化效应。通过使用非共价相互作用程序进行检查，从从头算分子动力学模拟获得的快照用于识别那些与铂配合物相互作用最强的溶剂分子。我们观察到基于狄拉克 - 库仑哈密顿量的全四分量矩阵狄拉克 - 科恩 - 沙姆方法（mDKS），结合KT2密度泛函以及对明确溶剂分子进行动态平均，具有令人满意的准确性。
