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A kinetics study of ligand substitution reaction on dinuclear platinum complexes: Stochastic versus deterministic approach
Author(s) -
Iioka Tatsuya,
Takahashi Satoshi,
Yoshida Yuichiro,
Matsumura Yoshihiro,
Hiraoka Shuichi,
Sato Hirofumi
Publication year - 2019
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.25588
Subject(s) - kinetics , rate equation , formalism (music) , pyridine , chemistry , ligand (biochemistry) , reaction rate constant , master equation , platinum , molecule , thermodynamics , substitution (logic) , chemical kinetics , reaction rate , rate of convergence , substitution reaction , computational chemistry , computer science , physics , organic chemistry , catalysis , quantum mechanics , biochemistry , receptor , channel (broadcasting) , art , musical , computer network , visual arts , quantum , programming language
The kinetics on a basic ligand substitution reaction on dinuclear platinum complexes [Pt(PEt 3 ) 2 PhPt(PEt 3 ) 2 ] 2+ and [Pt(PEt 3 ) 2 PhCOPhPt(PEt 3 ) 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.