Hydration of cis- and trans-platin: A pseudopotential treatment in the frame of a G3-type theory for platinum complexes
Hydration of cis- and trans-platin: A pseudopotential treatment in the frame of a G3-type theory for platinum complexes
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DOI：
10.1063/1.482036
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发表时间：
2000-07
影响因子：
4.4
通讯作者：
J. Burda;Michal Zeizinger;J. Šponer;J. Leszczynski
中科院分区：
文献类型：
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作者：
J. Burda;Michal Zeizinger;J. Šponer;J. Leszczynski
研究了铂配合物[PtCl42-−、铂(NH3)42+、顺式和反式铂-PtCl2(NH3)2]的水化反应。已经考虑了多达两个溶剂分子来取代配体。为了能够得出关于水化过程中pH变化的结论，在溶解过程中同时考虑了H2O和OH−物种。采用修正的Gauss3理论对铂配合物进行赝势处理。由于络合物中存在重元素，因此在G3处理方案上评估了由于自旋-轨道耦合和核-极化势而产生的额外稳定性。这种自旋-轨道耦合稳定化达到2-5千卡/摩尔，但不能定性地改变水化的偏好。与实验结果一致，中性的铂(NH_3)_2(OH)_2是顺铂和反铂水合反应中最稳定的络合物。
Hydration of selected platinum complexes [PtCl42−, Pt(NH3)42+, and cis- and trans-platin–PtCl2(NH3)2] have been studied. Up to two solvent molecules have been considered to replace the ligands. In order to be able to draw conclusions about pH changes in the course of the hydration process, both H2O and OH− species were considered in the solvating process. The modified Gaussian 3 theory was adapted for the pseudopotential treatment of platinum complexes. Since a heavy element was present in the complexes, an additional stabilization due to the spin–orbit coupling and core-polarization potentials have been evaluated above the scheme of a G3 treatment. This spin–orbit coupling stabilization amounts to 2–5 kcal/mol but does not qualitatively change the hydration preferences. In accord with the experiment, neutral Pt(NH3)2(OH)2 was found to be the most stable complex for hydration of both cis- and trans-platin.