Thioxoethenylidene (CCS) as a bridging ligand

Lorraine M. Caldwell; Anthony F. Hill; Robert Stranger; Richard N.L. Terrett; Kassetra M. Von Nessi; Jas S. Ward; Anthony C. Willis

doi:10.1021/om5011319

Thioxoethenylidene (CCS) as a bridging ligand

Lorraine M. Caldwell, Anthony F. Hill^*, Robert Stranger, Richard N.L. Terrett, Kassetra M. Von Nessi, Jas S. Ward, Anthony C. Willis

^*Corresponding author for this work

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

16 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	328-334
Number of pages	7
Journal	Organometallics
Volume	34
Issue number	1
DOIs	https://doi.org/10.1021/om5011319
Publication status	Published - 12 Jan 2015

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@article{259aed6cd09a44248abaa565cda17d5b,

title = "Thioxoethenylidene (CCS) as a bridging ligand",

abstract = "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.",

author = "Caldwell, \{Lorraine M.\} and Hill, \{Anthony F.\} and Robert Stranger and Terrett, \{Richard N.L.\} and \{Von Nessi\}, \{Kassetra M.\} and Ward, \{Jas S.\} and Willis, \{Anthony C.\}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2015",

month = jan,

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doi = "10.1021/om5011319",

language = "English",

volume = "34",

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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.

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 - https://www.scopus.com/pages/publications/84921021457

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 -

Thioxoethenylidene (CCS) as a bridging ligand

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