Controlling the Reactivity of the Boronyl Group in Platinum Complexes toward Cyclodimerization: A Theoretical Survey

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• 作者：Zhong Zhang ; Liang Pu ; Qian-shu Li ; R. Bruce King
• 刊名：Inorganic Chemistry
• 出版年：2015
• 出版时间：November 2, 2015
• 年：2015
• 卷：54
• 期：21
• 页码：10281-10286
• 全文大小：328K
• ISSN：1520-510X

文摘

A theoretical study of the cyclodimerization of (Cy<sub>3sub>P)<sub>2sub>Pt(BO)Br (1Br) and [(Cy<sub>3sub>P)<sub>2sub>Pt(BO)]<sup>+sup> (1) (Cy = cyclohexyl) suggests that the reactivity of the BO ligand is primarily controlled by M鈫怋O 蟽 donation. Therefore, increasing the electron density at the metal center through strong 蟽-donor and weak 蟺-acceptor ancillary ligands and a low formal metal oxidation state are suggested to reduce the polarity of the boronyl ligand and thus lower its reactivity toward cyclodimerization. The stable 1Br has lower Pt鈫怋O 蟽 donation and thus a less electrophilic boron atom, leading to a less polarized BO ligand. However, 1 is unstable in dichloromethane, since the dicationic dimer and transition state are highly stabilized by strong electrostatic interactions.