首页|Heterometallic Mg-Ni-Mg Complex Promoted Hydrosilylation of Alkenes:Catalytic Performance and Intermediates Characterization
Heterometallic Mg-Ni-Mg Complex Promoted Hydrosilylation of Alkenes:Catalytic Performance and Intermediates Characterization
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Heteronuclear metal complexes have played an increasingly important role in both small molecules activation and catalytic transfor-mation due to the potential metal-metal synergies.In this work,we reported that the well-defined Mg-Ni-Mg complex[(LMg)2Ni(C2H4)2]{L=[(DippNCMe)2CH]-,Dipp=2,6-iPr2C6H3} was capable of catalyzing the conversion of a diverse array of terminal alkenes to hydrosilylated products in onti-Markovnikov fashion using PhSiH3 as the silicon source.The stoichiometric reaction of het-erometallic Mg-Ni-Mg complex with one equivalent PhSiH3 obtained a silyl-nickel-monohydride complex[(LMg)2NiH(C2H4)(SiHPhEt)]featuring a Ni-Si-H-Mg interaction.Moreover,treatment of heterometallic Mg-Ni-Mg complex with three equivalents PhSiH3 provided the silyl-nickel-trihydride complex[(LMg)2NiH3(SiHPhEt)]with three hydride-bridged at Mg-Ni-Mg fragment.Further reactions of the resultant silyl-nickel complexes with alkenes,e.g.,ethylene and styrene,yielded the corresponding alkene-coordinated Mg-Ni-Mg complexes[(LMg)2Ni(C2H4)2],[(LMg)2NiH2(C2H4)]and[(LMg)2NiH2(CH2CHPh)],respectively,with the elimination of PhEtSiH2.Based on the control experiments,both silyl-nickel-monohydride and silyl-nickel-trihydride complexes were considered as active intermediates in the catalytic hydrosilylation reaction.
Key Laboratory of Organic Synthesis of Jiangsu Province,College of Chemistry,Chemical Engineering and Materials Science,Soochow University,Suzhou,Jiangsu 215123,China
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