Benzylic Complexes of Palladium(II): Bonding Modes and Pentacoordination for Steric Relief,Organometallics

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Benzylic Complexes of Palladium(II): Bonding Modes and Pentacoordination for Steric Relief
Organometallics ( IF 2.5 ) Pub Date : 2018-03-08 00:00:00 , DOI: 10.1021/acs.organomet.8b00065
Blanca Martín-Ruiz ₁ , Ignacio Pérez-Ortega ₁ , Ana C. Albéniz ₁

Affiliation

A large variety of α-(pentafluorophenylmethyl)benzylic palladium complexes with different ligands have been synthesized and characterized. Multinuclear NMR spectroscopic data allow to determine the σ- or η³-benzylic nature of the complexes in solution. The adoption of either coordination mode is a function of the number of ligands coordinated to palladium, and remarkably, the presence of bulky phosphines favors the adoption of a bidentate η³-benzylic mode and pentacoordinated palladium complexes. Experimental data and DFT calculations indicate that this five-coordination could alleviate the steric hindrance of two bulky cis phosphines. The benzylic complexes show a rich fluxional behavior that involves both ligand exchange and σ- to η³-benzylic interconversion.

中文翻译：

钯（II）的苯甲酸配合物：键的方式和Pentacoordination的立体救济。

已经合成并表征了多种具有不同配体的α-（五氟苯基甲基）苄基钯配合物。多核NMR光谱数据允许确定σ-或η ³溶液中的复合物的性质-benzylic。任一协调模式的通过是配位到钯的配体的数量的函数，并且显着地，体积大的膦的存在有利于在通过一个二齿η的³ -benzylic模式和五配位的钯络合物。实验数据和DFT计算表明，这种五配位可以减轻两个庞大的顺膦的空间位阻。苄基复合物显示，同时涉及配体交换和σ-至η丰富fluxional行为³-苄基互变。

更新日期：2018-03-09

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