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Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct Reactivity in C-H Bond Amination
Alternative Title三配位氮杂环卡宾配体钴(IV)(V)亚胺基络合物的合成、结构以及C-H键活化反应性质的研究
Zhang L(张龙); Liu YS(刘月盛); Deng L(邓亮)
2014
Source PublicationJ. Am. Chem. Soc.
Volume136Issue:44Pages:15525-15528
AbstractThe reaction of the cobalt(0) alkene complex [(IMes)Co(eta(2):eta(2))-dvtms)] (1) (IMes = 1,3-bis(1',3',5'-trimethylphenyl)imidazol-2-ylidene, dvtms = divinyltetramethyldisiloxane) with 2 equiv of DippN3 (Dipp = 2,6-diisopropylphenyl) afforded the cobalt(IV) imido complex [(IMes)Co(NDipp)2] (2), which could be oxidized by [Cp2Fe][BAr(F)(4)] (Ar(F) = 3,5-di(trifluoromethyl)phenyl) to give the cobalt(V) imido species [(IMes)Co(NDipp)2][BAr(F)(4)] (3). The molecular structures of all these complexes were established by single-crystal X-ray diffraction studies. Characterization data and theoretical calculations suggest ground spin states of S = (1)/2 and S = 0 for the cobalt(IV) and cobalt(V) species, respectively. When heated, the cobalt(IV) imido species was converted to a cobalt(II) diamido complex via an intramolecular C-H bond amination reaction, but the cobalt(V) species was stable under similar conditions. The different outcomes suggest that a high oxidation state does not guarantee C-H bond activation reactivity of late-transition-metal imido species.
Subject Area金属有机化学
DOI10.1021/ja509731z
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Indexed BySCI
Language英语
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Document Type期刊论文
Identifierhttp://ir.sioc.ac.cn/handle/331003/39124
Collection金属有机化学国家重点实验室
Corresponding AuthorDeng L(邓亮)
Affiliation中科院上海有机化学研究所
Recommended Citation
GB/T 7714
Zhang L,Liu YS,Deng L. Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct Reactivity in C-H Bond Amination[J]. J. Am. Chem. Soc.,2014,136(44):15525-15528.
APA 张龙,刘月盛,&邓亮.(2014).Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct Reactivity in C-H Bond Amination.J. Am. Chem. Soc.,136(44),15525-15528.
MLA 张龙,et al."Three-Coordinate Cobalt(IV) and Cobalt(V) Imido Complexes with N-Heterocyclic Carbene Ligation: Synthesis, Structure, and Their Distinct Reactivity in C-H Bond Amination".J. Am. Chem. Soc. 136.44(2014):15525-15528.
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