Dinitrogen Binding and Silylation by Bis(ketimino)carbazolide Complexes of Iron and Cobalt

Le résumé fourni par la source

We report the coordination chemistry of a bulky 1,8-bis(ketimino)carbazole (HL) ligand and the reactivity of the corresponding iron(II) and cobalt(II) chloride complexes [LFeCl] ( 1) and [LCoCl] ( 2 ). Upon one-electron reduction of 1 and 2 under a dinitrogen atmosphere, N 2 binds to the reduced metal centers to generate the corresponding square planar Fe(I) and Co(I) complexes [LFe(N 2 )] ( 3 ) and [LCo(N 2 )] ( 4·N 2 ), respectively. While further reduction of 3 generates the formally Fe(0) species [LFe(N 2 )] −, the reduction of 4·N 2 affords a three-coordinate [LCo(0)] complex ( 7 ) with the loss of N 2 from the metal center. Density functional theory (DFT) calculations suggest noninnocent behavior of the ligand. Both 3 and 4 can catalyze the silylation of N 2 using the combination of KC 8 and Me 3 SiCl reagents to produce N(SiMe 3 ) 3, where low temperature and batch addition significantly improve the yields to up to 52%.

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