Properties and Reactivities of Zwitterionic Platinum(II)-ate Complexes Generated by Transforming Coordination of an Alkyne－Bisphosphine Ligand
Properties and Reactivities of Zwitterionic Platinum(II)-ate Complexes Generated by Transforming Coordination of an Alkyne－Bisphosphine Ligand
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炔烃－双膦配体配位变换生成两性铂(II)配合物的性质和反应活性
DOI：
10.1021/acs.organomet.0c00759
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发表时间：
2021
期刊：
影响因子：
2.8
通讯作者：
and K. Ohe
中科院分区：
文献类型：
--
作者：
K. Okamoto;K. Sasakura;S. Funasaka;H. Watanabe;M. Suezaki;and K. Ohe
配位的炔-双膦配体与铂（II）前体产生的配体骨架中的结构重组，形成稳定的两性离子铂（II）络合物承载阴离子铂中心。这些配合物的结构性质和反应性进行了研究，使用X-射线晶体学分析，计算研究，和化学计量反应，涉及氧化加成和还原消除。这些研究表明，铂中心对烷基卤化物的亲核性增强促进了顺利的氧化加成，并且电荷再平衡加速了卤素阴离子从铂（IV）中间体的解离，这在碳-碳键形成步骤中是必不可少的。
Coordination of an alkyne–bisphosphine ligand with platinum(II) precursors produced a structural reorganization in the ligand backbone to form stable zwitterionic platinum(II) complexes bearing an anionic platinum center. The structural properties and reactivities of these complexes were investigated using X-ray crystallographic analyses, computational studies, and stoichiometric reactions involving oxidative addition and reductive elimination. These studies have shown that the enhanced nucleophilicity of the platinum center to alkyl halides promotes smooth oxidative addition and that the charge rebalance accelerates the dissociation of the halide anion from the platinum(IV) intermediate, which is essential in the carbon–carbon bond-forming step.