Homoleptic isocyanidemetalates of 4d- and 5d-transition metals: [Nb(CNXyl)6]-, [Ta(CNXyl)6]-, and derivatives thereof

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作者
Barybin, Mikhail V. [1 ,2 ]
Brennessel, William W. [1 ]
Kucera, Benjamin E. [1 ]
Minyaev, Mikhail E. [1 ]
Sussman, Victor J. [1 ]
Young Jr., Victor G. [1 ]
Ellis, John E. [1 ]
机构
[1] Department of Chemistry, University of Minnesota, Minneapolis, MN 55455, United States
[2] Department of Chemistry, University of Kansas, Lawrence, KS 66045, United States
来源
Journal of the American Chemical Society | 1600年 / 129卷 / 05期
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Treatment of [M(CO)6]-; M; Nb; Ta; with Ag +; I2 or NO+ in the presence of CNXyl provided [M(CNXyl)7]+; M(CNXyl)6I; or cis-[M(CNXyl) 4(NO)2]+; which are isocyanide analogues of the unknown carbonyl complexes [M(CO)7]+; M(CO)6I; or cis-[M(CO)4(NO)2]+; respectively. Reduction of M(CNXyl)6I by cesium graphite gave the respective Cs[M(CNXyl)6; which have been structurally characterized and represent the first isolable homoleptic isocyanidemetalates for second or third row transition metals. Nitrosylation of [Ta(CNXyl)6]- affords a rare example of a mononitrosyl tantalum complex; Ta(CNXyl); 5NO; which is an isocyanide analogue of the unknown Ta(CO) 5NO. This study emphasizes; inter alia; the remarkable versatility of the CNXyl ligand compared to CO in stabilizing various electronic environments at heavier group 5 metal centers. © 2007 American Chemical Society;
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页码:1141 / 1150
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