由亚磷烷ONP配体支撑的NiII配合物：合成及催化C=C和C=O键硅氢化反应

IF 6.4 1区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Frontiers Pub Date : 2025-10-16 DOI:10.1039/d5qi01895a

Ingrid Popovici, Thomas F. Akwright Arcilla, Sophie Bourcier, Nicolas Casaretto, Vincent Gandon, Audrey Auffrant

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引用次数: 0

摘要

合成了一种原始的ONP亚磷烷配体，配位成[NiX2(DME)] （X=Cl, Br）。相应的配合物（2X， X=Cl, Br）被分离出来，并通过多核磁共振波谱和X射线晶体学进行了表征。所收集的数据表明，不同的几何形状共存于室温下的溶液中。2Cl被证明是一种高效的硅氢化催化剂，在1 mol %的SiH2Ph2和1 mol %的tBuOK的存在下，可以在1 h内对大多数底物进行高收率的C=C和C=O键还原。此外，还观察到9个烯酮的C=O键选择性转化为硅醚键。因此，与先前描述的Ni催化剂相比，2Cl表现出相当独特的催化行为。有关机理的实验和理论研究表明，Ni-H配合物的参与。结果表明，该反应的最高过渡态仅为19.0 kcal mol-1，是由有利的热力学驱动的。

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NiII complex supported by an iminophosphorane ONP ligand: Synthesis and catalytic C=C and C=O bonds hydrosilylation

An original ONP iminophosphorane ligand was synthesised and coordinated to [NiX2(DME)] (X=Cl, Br). The corresponding complexes (2X, X=Cl, Br) were isolated and characterised among others by multinuclear NMR spectroscopy and X-ray crystallography. The collected data suggest that different geometries coexist in solution at room temperature. 2Cl proved to be an efficient hydrosilylation catalyst able to perform at a loading of 1 mol % in presence of one equivalent SiH2Ph2 and 1 mol % of tBuOK, the reduction of C=C and C=O bonds in high yield in 1 h for most substrates. Moreover, the selective conversion of C=O bond to silylether linkage was observed for nine enones. Therefore, 2Cl presents a rather unique catalytic behaviour compared to previously described Ni catalysts. Both experimental and theoretical investigations regarding the mechanism suggest the involvement of a Ni-H complex. The computed mechanism presents a highest-lying transition state at only 19.0 kcal mol-1 and shows that the reaction is driven by the favorable thermodynamics.

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