Departament de Química and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universitat Autònoma de Barcelona, 08193, Cerdanyola del Valles, Barcelona, Catalonia, Spain.
Chemistry. 2021 Nov 17;27(64):15973-15980. doi: 10.1002/chem.202102250. Epub 2021 Oct 13.
The reductive elimination on [(Me P) Pt(MeOH)(CH ) ] , 2P, complex performed in MeOH solution and inside a [Ga L ] metallocage are computationally analysed by mean of QM and MD simulations and compared with the mechanism of gold parent systems previously reported [Et PAu(MeOH)(CH ) ] , 2Au. The comparative analysis between the encapsulated Au(III) and Pt(IV)-counterparts shows that there are no additional solvent MeOH molecules inside the cavity of the metallocage for both systems. The Gibbs energy barriers for the 2P reductive elimination calculated at DFT level are in good agreement with the experimental values for both environments. The effect of microsolvation and encapsulation on the rate acceleration are evaluated and shows that the latter is far more relevant, conversely to 2Au. Energy decomposition analysis indicates that the encapsulation is the main responsible for most of the energy barrier reduction. Microsolvation and encapsulation effects are not equally contributing for both metal systems and consequently, the reasons of the rate acceleration are not the same for both metallic systems despite the similarity between them.
[(Me P)Pt(MeOH)(CH ) ], 2P，配合物在甲醇溶液中和 [Ga L ] 金属笼内的还原消除反应通过 QM 和 MD 模拟进行了计算分析，并与之前报道的金母体体系[Et PAu(MeOH)(CH ) ], 2Au 的反应机制进行了比较。对包裹的 Au(III)和 Pt(IV)的对比分析表明，对于这两个体系，金属笼的腔内都没有额外的溶剂 MeOH 分子。在 DFT 水平上计算的 2P 还原消除的吉布斯能垒与两种环境的实验值非常吻合。还评估了微溶剂化和包裹对速率加速的影响，表明后者更为相关，与 2Au 相反。能量分解分析表明，包裹是导致大部分能垒降低的主要原因。微溶剂化和包裹效应对两种金属体系的贡献并不相同，因此，尽管它们之间存在相似性，但两种金属体系的速率加速原因并不相同。
