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首页> 外文期刊>Chemistry: A European journal >'Roll-over' Cyclometalation of 2,2 '-Bipyridine Platinum(II) Complexes in the Gas Phase: A Combined Experimental and Computational Study
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'Roll-over' Cyclometalation of 2,2 '-Bipyridine Platinum(II) Complexes in the Gas Phase: A Combined Experimental and Computational Study

机译：气相中2,2'-联吡啶铂（II）配合物的“翻滚”环金属化：实验和计算研究相结合

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摘要

In a combined experimental/computational investigation, the gasphase behavior of cationic [Pt(bipy)(CH3)((CH3)(2)S)](+) (1) (bipy=2,2'-bipyridine) has been explored. Losses of CH, and (CH3)(2)S from 1. result in the formation of a cyclometalated 2,2'-bipyrid-3-yl species [Pt(bipy-H)](+) (2). As to the mechanisms of ligand evaporation, detailed labeling experiments complemented by DFF-based computations reveal that the reaction follows the mechanistically intriguing "roll-over" cyclometalation path in the course of which a hydrogen atom from the C(3)-position is combined with the Pt-bound methyl group to produce CH, Activation of a C-H-bond of the (CH3)(2)S ligand occurs as well, but is less favored (35% versus 65%) as compared to the C(3)-H bond activation of bipy. In addition, the thermal ion/molecule reactions of [Pt(bipy-H)](+) with (CH3)(2)S have been examined, and for the major pathway, that is, the dehydrogenative coupling of the two methyl groups to form C2H4, a mechanism is suggested that is compatible with the experimental and computational findings. A hallmark of the gas-phase chemistry of [Pt(bipy-H)](+) with the incoming (CH3)(2)S ligand is the exchange of one (and only one) hydrogen atom of the bipy fragment with the C-H bonds of dimethylsulfide in a reversible "roll-over" cyclometalation reaction. The Pt-II-mediated conversion of (CH3)(2)S to C2H4, may serve as a model to obtain mechanistic insight in the dehydrosulfurization of sulfur-containing hydrocarbons.
机译：在组合的实验/计算研究中，已研究了阳离子[Pt（bipy）（CH3）（（CH3）（2）S）]（+）（1）（bipy = 2,2'-bipyridine）的气相行为。 CH和1中的（CH3）（2）S的损失导致形成环金属化的2,2'-联吡啶-3-基物质[Pt（bipy-H）]（+）（2）。关于配体蒸发的机理，详细的标记实验辅以基于DFF的计算方法揭示，该反应遵循机械上有趣的“翻转”环金属化路径，在此过程中，来自C（3）-位的氢原子被合并与Pt结合的甲基基团产生CH时，也会发生（CH3）（2）S配体的CH键活化，但与C（3）相比，其受青睐程度较低（35％对65％） Bipy的-H键活化。此外，还研究了[Pt（bipy-H）]（+）与（CH3）（2）S的热离子/分子反应，并且研究了主要途径，即两个甲基的脱氢偶联为了形成C 2 H 4，提出了一种与实验和计算结果兼容的机理。 [Pt（bipy-H）]（+）与进入的（CH3）（2）S配体的气相化学反应的一个标志是，Bipy片段的一个（只有一个）氢原子与CH交换可逆的“翻转”环金属化反应中的二甲基硫键。由Pt-II介导的（CH3）（2）S到C2H4的转化可以用作在含硫烃的脱硫过程中获得机械洞察力的模型。

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