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N-Aryl β-diiminate complexes of the platinum metals

机译:铂金属的N-芳基β-二氨基配合物

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摘要

This perspective summarizes the chemistry of platinum metal complexes of β-diiminate ligands bearing aryl groups at the nitrogen atoms. While β-diiminate ligands mostly coordinate in a κ~2-N,N′ mode, palladium complexes have a tendency to rearrange to C-bound structures (κ~2-N,C or μ-N,N′:C). Diiminate ligands are remarkably effective at stabilizing coordinatively unsaturated metal centers, and the resulting reactive complexes often activate C-H bonds even of relatively unreactive substrates (ethers, alkanes). However, the ligands are not completely innocent: addition of H_2, O_2, olefins, alkynes and phospha-alkynes across M-Cβ has been observed for several of the platinum metals, and may even be relevant to catalytic activity. A comparison with related ligands (triazapentadienyl, formazanate, bis(phosphinimino)methanate) suggests that the β-diiminate ligand represents a lucky combination of steric rigidity and strong σ (and π?) donor character, making it an ideal platform for mechanistic studies of catalytic reactions.
机译:该观点总结了在氮原子上带有芳基的β-二氨基配体的铂金属配合物的化学性质。尽管β-二氨基配体主要以κ〜2-N,N'模式进行配位,但钯配合物却倾向于重排至C结合结构(κ〜2-N,C或μ-N,N':C)。二价配体在稳定配位不饱和金属中心方面非常有效,并且所得的反应性络合物甚至即使相对不反应的底物(醚,烷烃)也经常激活C-H键。但是,配体并非完全是纯的:对于几种铂金属,已经观察到在M-Cβ上添加H_2,O_2,烯烃,炔烃和膦炔烃,甚至可能与催化活性有关。与相关配体(三氮杂戊二烯基,甲酸酯,双(膦基氨基)甲酸酯)的比较表明,β-二氨基配体代表了空间刚度和强大的σ(和π?)供体特征的幸运组合,使其成为研究分子机理的理想平台催化反应。

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