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Synthesis, Structure, and Reactivity of Low-Spin Cobalt(II) Imido Complexes [(Me3P)3Co(NAr)]
Yang Liu1, Jingzhen Du1, Liang Deng1
1State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences , 345 Lingling Road, Shanghai 200032, P. R. China.
Abstract:
The reactions of [Co(PMe3)4] with the bulky organic azides, DippN3 and DmpN3 [Dipp, 2,6-diisopropylphenyl; Dmp, 2,6-di(2',4',6'-trimethylphenyl)phenyl], afforded the cobalt(II) terminal imido complexes [(Me3P)3Co(NAr)] (Ar = Dipp, 1; Dmp, 2). The cobalt imido complexes in their solid states show trigonal pyramidal coordination geometry and long Co-N(imido) separations (ca. 1.71 Å). Spectroscopic characterization and theoretical studies indicated their low-spin cobalt(II) nature. Reactivity studies on 1 revealed its nitrene-transfer reactions with PMe3 and CO, the imido/oxo and imido/sulfido exchange reactions with PhCHO and CS2, and the single-electron oxidation reaction by ferrocenium cation to form cobalt(III) imide.
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