TY - JOUR
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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U2 - 10.1021/ja065964q
DO - 10.1021/ja065964q
M3 - Article
C2 - 17263395
AN - SCOPUS:33846842427
SN - 0002-7863
VL - 129
SP - 1141
EP - 1150
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 5
ER -