Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functiona...Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.展开更多
基金supported by the Basic Science Center of Transformation Chemistry of Key Components of Air,National Natural Science Foundation of China(no.21988101)M.Z.acknowledges China Postdoctoral Science Foundation(no.2019M650294)+1 种基金L.Z.acknowledges the financial support from NSFC(nos.21973044 and 21703099)Natural Science Foundation of Jiangsu Province for Youth(no.BK20170964)。
文摘Cobalt-bis(dinitrogen)complexes[LCo(N_(2))_(2)]−(3,4)with simple and commercially available bidentate phosphine ligands(L:Cy_(2)PCH_(2)CH_(2)PCy_(2))were synthesized and structurally characterized.Further N2 functionalization by treating the complex 3b with i Pr_(3)SiCl afforded the first structurally characterized cobalt diazenido complex 5.These complexes 3–5 were found to be effective catalysts for the transformation of N2 into N(SiMe_(3))_(3).The electronic structure of the cobalt diazenido complex 5 is supported by quantum computational calculations based on stateof-the-art energy decomposition analysis(EDA)in conjunction with the natural orbitals for chemical valence(NOCV)method.
