Synthesis, Structure, and Reactivity of Low-Spin Cobalt(II) Imido Complexes [(Me3P)(3)Co(NAr)]
Synthesis, Structure, and Reactivity of Low-Spin Cobalt(II) Imido Complexes [(Me3P)(3)Co(NAr)]
复制标题
低自旋钴(II)亚氨基配合物[(Me3P)(3)Co(NAr)]的合成、结构和反应性
DOI：
10.1021/acs.inorgchem.7b00941
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发表时间：
2017
影响因子：
4.6
通讯作者：
Deng Liang
中科院分区：
文献类型：
--
作者：
Liu Yang;Du Jingzhen;Deng Liang
[Co(PMe3)4] 与大体积有机叠氮化物 DippN3 和 DmpN3[Dipp, 2,6-二异丙基苯基； Dmp, 2,6-二(2',4',6'-三甲基苯基)苯基]，得到钴(II)末端亚氨基配合物[(Me3P)3Co(NAr)]（Ar = Dipp,1；Dmp,2）。固态钴亚氨基配合物显示出三角锥配位几何形状和长Co-N（亚氨基）间隔（约1.71 Å）。光谱表征和理论研究表明了它们的低自旋钴（II）性质。反应性研究揭示了其与PMe3和CO的氮宾转移反应，与PhCHO和CS2的亚氨基/氧代和亚氨基/硫代交换反应，以及二茂铁阳离子形成亚胺钴(III)的单电子氧化反应。
The reactions of [Co(PMe3)4] with the bulky organic azides, DippN3and 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 on1revealed its nitrene-transfer reactions with PMe3and 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.