4d 和 5d 过渡金属的同配异腈基金属酸盐：[Nb(CNXyl)₆]⁻、[Ta(CNXyl)₆]⁻及其衍生物。
Homoleptic isocyanidemetalates of 4d- and 5d-transition metals: [Nb(CNXyl)(6)](-), [Ta(CNXyl)(6)](-), and derivatives thereof.
作者信息
Barybin Mikhail V, Brennessel William W, Kucera Benjamin E, Minyaev Mikhail E, Sussman Victor J, Young Victor G, Ellis John E
机构信息
Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.
出版信息
J Am Chem Soc. 2007 Feb 7;129(5):1141-50. doi: 10.1021/ja065964q.
Treatment of M(CO)(6), M = Nb, Ta, with Ag(+), I(2) or NO(+) in the presence of CNXyl provided M(CNXyl)(7), M(CNXyl)(6)I, or cis-M(CNXyl)(4)(NO)(2), which are isocyanide analogues of the unknown carbonyl complexes M(CO)(7), M(CO)(6)I, or cis-M(CO)(4)(NO)(2), respectively. Reduction of M(CNXyl)(6)I 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)(5)NO, which is an isocyanide analogue of the unknown Ta(CO)(5)NO. 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.
在存在 CNXyl 的情况下，用 Ag⁺、I₂ 或 NO⁺ 处理 [M(CO)₆]⁻（M = Nb、Ta），得到了 [M(CNXyl)₇]⁺、M(CNXyl)₆I 或顺式 - [M(CNXyl)₄(NO)₂]⁺，它们分别是未知羰基配合物 [M(CO)₇]⁺、M(CO)₆I 或顺式 - [M(CO)₄(NO)₂]⁺ 的异氰化物类似物。用铯石墨还原 M(CNXyl)₆I 得到相应的 Cs[M(CNXyl)₆]，其结构已得到表征，并且代表了第二或第三排过渡金属的首个可分离的同配异氰基金属酸盐。[Ta(CNXyl)₆]⁻ 的亚硝基化提供了一个罕见的单亚硝基钽配合物 Ta(CNXyl)₅NO 的例子，它是未知的 Ta(CO)₅NO 的异氰化物类似物。这项研究尤其强调了与 CO 相比，CNXyl 配体在稳定较重的第 5 族金属中心的各种电子环境方面具有显著的多功能性。
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