期刊
INORGANIC CHEMISTRY
卷 56, 期 14, 页码 8278-8286出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.7b00941
关键词
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资金
- National Key Research and Development Program [2016YFA0202900]
- National Natural Science Foundation of China [21690062, 21421091, 21432001]
- Strategic Priority Research Program of the Chinese Academy of Sciences [XDB20000000]
The reactions of [Co(PMe3)(4)] with the bulky organic azides, DippN(3) and DmpN(3) [Dipp, 2,6-diisopropylphenyl; Dmp, 2,6-di(2',4',6'-trimethylphenyl)phenyl], afforded the cobalt(II) terminal imido complexes [(Me3P)(3)Co(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 angstrom). 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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