A Kinetics Study of Ligand Substitution Reaction on Dinuclear Platinum Complexes: Stochastic Versus Deterministic Approach
A Kinetics Study of Ligand Substitution Reaction on Dinuclear Platinum Complexes: Stochastic Versus Deterministic Approach
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双核铂配合物上配体取代反应的动力学研究：随机方法与确定性方法
DOI：
10.1002/jcc.25588
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发表时间：
2019
影响因子：
3
通讯作者：
and H. Sato
中科院分区：
文献类型：
--
作者：
T. Iioka;S. Takahashi;Y. Yoshida;Y. Matsumura;S. Hiraoka;and H. Sato
研究了双核铂配合物[Pt(PEt3)2PhPt(PEt3)2]2+和[Pt(PEt3)2PhCOPhPt(PEt3)2]2+与配体吡啶和3‐氯吡啶的碱性配体取代反应动力学。这是自组装的一个基本步骤，并且时间演变已经通过一种新的实验技术观察到，QASAP（自组装过程的定量分析），这是由hiroka的团队最近开发的。通过主方程的数值计算，我们成功地用一个简单的反应模型确定了反应速率常数。此外，还揭示了化学反应中产生和消耗的所有中间组分的时间演化，包括实验中未观察到的中间组分。将随机算法计算的特定化学物质存在率的收敛性与基于速率方程的确定性公式计算的存在率的收敛性进行了比较，揭示了存在率与组成分子数量的明显依赖关系。©2018 Wiley期刊公司
The kinetics on a basic ligand substitution reaction on dinuclear platinum complexes [Pt(PEt3)2PhPt(PEt3)2]2+and [Pt(PEt3)2PhCOPhPt(PEt3)2]2+, with the ligands pyridine and 3‐chloropyridine, is studied. This is a fundamental step in a self‐assembly, and the time evolution has been observed with a new experimental technique, QASAP (quantitative analysis of self‐assembly process), which is recently developed by Hiraoka's group. As a result of numerical calculations based on master equation, we succeed in specifying the reaction rate constants with a simple reaction model. In addition, the time evolutions of all the intermediate components produced and consumed in chemical reaction are revealed, including those unobserved in the experiments. The convergence behavior of the existence ratios of specific chemical species calculated with the stochastic algorithm method is compared with those obtained from deterministic formalism based on rate equations, revealing a clear dependence on the number of constituent molecules. © 2018 Wiley Periodicals, Inc.