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

Mikhail V Barybin; William W Brennessel; Benjamin E Kucera; Mikhail E Minyaev; Victor J Sussman; Victor G Young Jr; John E Ellis

doi:10.1021/ja065964q

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

J Am Chem Soc. 2007 Feb 7;129(5):1141-50. doi: 10.1021/ja065964q.

Authors

Mikhail V Barybin¹, William W Brennessel, Benjamin E Kucera, Mikhail E Minyaev, Victor J Sussman, Victor G Young Jr, John E Ellis

Affiliation

¹ Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455, USA.

PMID: 17263395
DOI: 10.1021/ja065964q

Abstract

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.