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; John E Ellis

doi:10.1021/ja065964q

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, John E Ellis

Chemistry (Twin Cities)

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	1141-1150
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	129
Issue number	5
DOIs	https://doi.org/10.1021/ja065964q
State	Published - Feb 7 2007

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

abstract = "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.",

author = "Barybin, {Mikhail V.} and Brennessel, {William W.} and Kucera, {Benjamin E.} and Minyaev, {Mikhail E.} and Sussman, {Victor J.} and Young, {Victor G} and Ellis, {John E}",

year = "2007",

month = feb,

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doi = "10.1021/ja065964q",

language = "English (US)",

volume = "129",

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journal = "Journal of the American Chemical Society",

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T1 - Homoleptic isocyanidemetalates of 4d- and 5d-transition metals

T2 - [Nb(CNXyl)6]-, [Ta(CNXyl)6]-, and derivatives thereof

AU - Barybin, Mikhail V.

AU - Brennessel, William W.

AU - Kucera, Benjamin E.

AU - Minyaev, Mikhail E.

AU - Sussman, Victor J.

AU - Young, Victor G

AU - Ellis, John E

PY - 2007/2/7

Y1 - 2007/2/7

N2 - 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.

AB - 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.

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

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