An original ONP iminophosphorane ligand was synthesised and coordinated to[NiX_(2)(DME)](X=Cl,Br).The corresponding complexes(2X,X=Cl,Br)were isolated and characterised among others by multinuclear NMR spectroscopy an...An original ONP iminophosphorane ligand was synthesised and coordinated to[NiX_(2)(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 the presence of one equivalent of SiH_(2)Ph_(2) and 1 mol%of tBuOK,with the reduction of C=C and C=O bonds in high yield in 1 h for most substrates.Moreover,the selective conversion of the C=O bond to a 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 favorable thermodynamics.展开更多
基金granted access to the HPC resources of CINES under allocation 2020-A0070810977 made by GENCI to VGThe Agence Nationale de la Recherche(ANR-21-CE07-0026)is acknowledged for funding the LYMACATO project,and the RESOMAG platform for access to NMR instruments,as well as GDR Phosphore for gathering the community of P-chemists in France.
文摘An original ONP iminophosphorane ligand was synthesised and coordinated to[NiX_(2)(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 the presence of one equivalent of SiH_(2)Ph_(2) and 1 mol%of tBuOK,with the reduction of C=C and C=O bonds in high yield in 1 h for most substrates.Moreover,the selective conversion of the C=O bond to a 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 favorable thermodynamics.
