Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes,European Journal of Inorganic Chemistry

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Reactions of Schiff Base‐Substituted Diselenides and ‐tellurides with Ni(II), Pd(II) and Pt(II) Phosphine Complexes
European Journal of Inorganic Chemistry ( IF 2.2 ) Pub Date : 2020-09-08 , DOI: 10.1002/ejic.202000750
Maximilian Roca Jungfer ₁ , Ernesto Schulz Lang ₂ , Ulrich Abram ₃

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The salicylidene Schiff bases of bis(2‐aminophenyl)diselenide and ‐ditelluride react with [M^IICl₂(PPh₃)₂] (M = Ni, Pt) or [Pd^II(OAc)₂(PPh₃)₂] with formation of square‐planar complexes with the general formulae [M^II(L^Y)(PPh₃)] (M = Ni, Pd, Pt, Y = Se, Te). The ligands coordinate to the metals as tridentate {O,N,Se/Te} chelates. The reduction of the dichalcogenides and the formation of the chalcogenolato ligands occurs in situ by released PPh₃ ligands. A mechanism for such reactions has been derived from the experimental data with the aid of DFT calculations. It suggests a higher polarization of the dichalcogenide bond with partial charge separation upon coordination to a metal centre, which therefore facilitates the cleavage of the dichalcogenide bond with PPh₃. In accordance with the proposed mechanism, best yields are obtained with a strict exclusion of oxygen, but in the presence of water.

中文翻译：

Schiff碱取代的二硒化物和碲化物与Ni（II），Pd（II）和Pt（II）膦配合物的反应

双（2-氨基苯基）二硒化物和-二碲化物的水杨基席夫碱与[M ^II Cl ₂（PPh ₃）₂ ]（M = Ni，Pt）或[Pd ^II（OAc）₂（PPh ₃）₂ ]与通式[M ^II（L ^Y）（PPh ₃）]（M = Ni，Pd，Pt，Y = Se，Te）形成方平面配合物。配体与金属配位成三齿{O，N，Se / Te}螯合物。通过释放的PPh ₃原位发生二氰化物的还原和硫属元素生成。配体。借助于DFT计算，已经从实验数据中得出了这种反应的机理。这表明在与金属中心配位时，二硫代氰化物键具有更高的极化和部分电荷分离，因此有助于二硫代氰化物键与PPh ₃的裂解。根据提出的机制，在严格排除氧气的情况下，但在有水的情况下，可获得最佳产量。

更新日期：2020-09-08

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