Silyl cobalt species are putative intermediates in cobalt-catalyzed transformations of hydrosilanes.However,their reactivity has remained poorly understood.Reported here is the investigation on four-coordinate disilyl...Silyl cobalt species are putative intermediates in cobalt-catalyzed transformations of hydrosilanes.However,their reactivity has remained poorly understood.Reported here is the investigation on four-coordinate disilyl Co(Ⅱ)complexes with N-hetereocyclic carbene ligation.The reactions of[(ICy)_(2)Co(vtms)](ICy=1,3-dicyclohexylimidazol-2-ylidene,vtms=vinyltrimethylsilane)with primary and secondary hydrosilanes(3 equiv.)furnish the four-coordinate disilyl complexes[trans-(ICy)_(2)Co(SiHRR')_(2)](SiHRR'=SiH_(2)Mes,1;SiH_(2)Ph,2;SiH_(2)Cy,3;SiHPh_(2),4;SiHEt_(2),5)in moderate to good yields.The structures of 1,2 and 4 were established by single-crystal X-ray diffraction.Solution magnetic susceptibility measurement and EPR spectroscopy indicate their low-spin nature(S=1/2).Reactivity studies on 4 led to the establishment of the conversions of 4 to the disilyl dihydride Co(Ⅲ)complex[K(THF)][(ICy)_(2)Co(H)_(2)(SiHPh_(2))_(2)]_n(6)and the fluorosilyl Co(Ⅱ)complex[(ICy)_(2)Co(THF)(SiFPh_(2))][BF_(4)](7)when 4 was treated with excess amount of K and AgBF_(4),respectively,in THF.These conversions hint at the high activity of low-valent and high-valent disilyl cobalt species[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(1-)and[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(2+).Complex 4 is reactive toward terminal alkynes,but inert toward alkenes and internal alkynes.The reactions of 4 with terminal alkynes CyC≡CH and Me_(3)SiC≡CH(3 equiv.)yield the Co(Ⅱ)complexes[(ICy)_(2)Co(C≡CCy)_(2)](8)and[(ICy)_(2)Co(C≡CSiMe_(3))((SiMe_(3))C=CH_(2))](9),respectively,along with H_(2)SiPh_(2)and alkynylsilanes RC≡CSiHPh_(2)(R=Cy,SiMe_(3)),whereas the reaction with 4-CF_(3)C_(6)H_(4)C≡CH(3 equiv.)produce[(ICy)_(2)Co(C≡CAr)((Ar)C=CH(SiHPh_(2))C=CHAr)](Ar=4-CF_(3)C_(6)H_(4))(10)and H_(2)SiPh_(2).These reactions are proposed to involveσ-bond metathesis reactions between alkyne C(sp)-H bonds and Co-Si bonds in 4.Complexes 6–10 have been characterized by NMR spectroscopy,X-ray diffraction study,and elemental analysis.展开更多
基金supported by the National Key Research and Development Program of the Ministry of Science and Technology of China(No.2021YFA1500203)Natural Science Foundation of China(Nos.22231010,22061160464,21821002,and 22201290)Shanghai Sailing Program(No.22YF1458200)。
文摘Silyl cobalt species are putative intermediates in cobalt-catalyzed transformations of hydrosilanes.However,their reactivity has remained poorly understood.Reported here is the investigation on four-coordinate disilyl Co(Ⅱ)complexes with N-hetereocyclic carbene ligation.The reactions of[(ICy)_(2)Co(vtms)](ICy=1,3-dicyclohexylimidazol-2-ylidene,vtms=vinyltrimethylsilane)with primary and secondary hydrosilanes(3 equiv.)furnish the four-coordinate disilyl complexes[trans-(ICy)_(2)Co(SiHRR')_(2)](SiHRR'=SiH_(2)Mes,1;SiH_(2)Ph,2;SiH_(2)Cy,3;SiHPh_(2),4;SiHEt_(2),5)in moderate to good yields.The structures of 1,2 and 4 were established by single-crystal X-ray diffraction.Solution magnetic susceptibility measurement and EPR spectroscopy indicate their low-spin nature(S=1/2).Reactivity studies on 4 led to the establishment of the conversions of 4 to the disilyl dihydride Co(Ⅲ)complex[K(THF)][(ICy)_(2)Co(H)_(2)(SiHPh_(2))_(2)]_n(6)and the fluorosilyl Co(Ⅱ)complex[(ICy)_(2)Co(THF)(SiFPh_(2))][BF_(4)](7)when 4 was treated with excess amount of K and AgBF_(4),respectively,in THF.These conversions hint at the high activity of low-valent and high-valent disilyl cobalt species[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(1-)and[trans-(ICy)_(2)Co(SiHPh_(2))_(2)]^(2+).Complex 4 is reactive toward terminal alkynes,but inert toward alkenes and internal alkynes.The reactions of 4 with terminal alkynes CyC≡CH and Me_(3)SiC≡CH(3 equiv.)yield the Co(Ⅱ)complexes[(ICy)_(2)Co(C≡CCy)_(2)](8)and[(ICy)_(2)Co(C≡CSiMe_(3))((SiMe_(3))C=CH_(2))](9),respectively,along with H_(2)SiPh_(2)and alkynylsilanes RC≡CSiHPh_(2)(R=Cy,SiMe_(3)),whereas the reaction with 4-CF_(3)C_(6)H_(4)C≡CH(3 equiv.)produce[(ICy)_(2)Co(C≡CAr)((Ar)C=CH(SiHPh_(2))C=CHAr)](Ar=4-CF_(3)C_(6)H_(4))(10)and H_(2)SiPh_(2).These reactions are proposed to involveσ-bond metathesis reactions between alkyne C(sp)-H bonds and Co-Si bonds in 4.Complexes 6–10 have been characterized by NMR spectroscopy,X-ray diffraction study,and elemental analysis.
