TY - JOUR
T1 - Thioxoethenylidene (CCS) as a bridging ligand
AU - Caldwell, Lorraine M.
AU - Hill, Anthony F.
AU - Stranger, Robert
AU - Terrett, Richard N.L.
AU - Von Nessi, Kassetra M.
AU - Ward, Jas S.
AU - Willis, Anthony C.
N1 - Publisher Copyright:
© 2014 American Chemical Society.
PY - 2015/1/12
Y1 - 2015/1/12
N2 - The reaction of [Mo(=CBr)(CO)2(Tp)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with [Fe2(μ-SLi)2(CO)6] affords, inter alia, the unsymmetrical binuclear thioxoethenylidene complex [Mo2(μ,(C):η2(C′S)-CCS)(CO)4(Tp)2], which may be more directly obtained from [Mo(=CBr)(CO)2(Tp)] and Li2S. The reaction presumably proceeds via the intermediacy of the bis(alkylidynyl)thioether complex S{C=Mo(CO)2(Tp)}2, which was, however, not directly observed but explored computationally and found to lie 78.6 kJ mol-1 higher in energy than the final thioxoethenylidene product. Computational interrogation of the molecules [M2(μ-C2S)(CO)2(Tp)2] (M = Mo, W, Re, Os) reveals three plausible coordination modes for a thioxoethenylidene bridge which involve a progressive strengthening of the C-C bond and weakening of the M-C and M-S bonds, as might be expected from simple effective atomic number considerations.
AB - The reaction of [Mo(=CBr)(CO)2(Tp)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with [Fe2(μ-SLi)2(CO)6] affords, inter alia, the unsymmetrical binuclear thioxoethenylidene complex [Mo2(μ,(C):η2(C′S)-CCS)(CO)4(Tp)2], which may be more directly obtained from [Mo(=CBr)(CO)2(Tp)] and Li2S. The reaction presumably proceeds via the intermediacy of the bis(alkylidynyl)thioether complex S{C=Mo(CO)2(Tp)}2, which was, however, not directly observed but explored computationally and found to lie 78.6 kJ mol-1 higher in energy than the final thioxoethenylidene product. Computational interrogation of the molecules [M2(μ-C2S)(CO)2(Tp)2] (M = Mo, W, Re, Os) reveals three plausible coordination modes for a thioxoethenylidene bridge which involve a progressive strengthening of the C-C bond and weakening of the M-C and M-S bonds, as might be expected from simple effective atomic number considerations.
UR - http://www.scopus.com/inward/record.url?scp=84921021457&partnerID=8YFLogxK
U2 - 10.1021/om5011319
DO - 10.1021/om5011319
M3 - Article
SN - 0276-7333
VL - 34
SP - 328
EP - 334
JO - Organometallics
JF - Organometallics
IS - 1
ER -