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==Preparation== |
==Preparation== |
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The main challenge for the preparation of thiocarbonyl complexes arises from the non-availability of [[carbon monosulfide]]. |
The main challenge for the preparation of thiocarbonyl complexes arises from the non-availability of [[carbon monosulfide]]. Thus, the CS ligand is often extruded from thiocarbonyl-containing precursors. One example involves [[thiophosgene]], which reacts with [[disodium tetracarbonylferrate]]: |
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:Na<sub>2</sub>Fe(CO)<sub>4</sub> + CSCl<sub>2</sub> → Fe(CO)<sub>4</sub>CS + 2 NaCl |
:Na<sub>2</sub>Fe(CO)<sub>4</sub> + CSCl<sub>2</sub> → Fe(CO)<sub>4</sub>CS + 2 NaCl |
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Instead of thiophosgene, chlorothioformates (ClC(S)OAr) have also been used as a source of CS ligand. The thiocarbonyl analogue of [[Vaska’s complex]] is prepared in this way.<ref>{{cite |
Instead of thiophosgene, chlorothioformates (ClC(S)OAr) have also been used as a source of CS ligand. The thiocarbonyl analogue of [[Vaska’s complex]] is prepared in this way.<ref>{{cite |
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|title= Chlorothiocarbonyl-bis(triphenylphosphine)iridium(I) [IrCl(CS)(PPh<sub>3</sub>)<sub>2</sub>] |
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|title= Inorganic Syntheses |
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|author1=Hill, A. F. |author2=Wilton-Ely, J. D. E. T. |
|author1=Hill, A. F. |author2=Wilton-Ely, J. D. E. T. |
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|=Inorganic Syntheses |
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|year= 2002 |volume= 33 |pages= 244–245 |
|year= 2002 |volume= 33 |pages= 244–245 |
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:{{chem2|RhCl(PPh3)3 + CS2 -> RhCl(CS2)(PPh3)3}} |
:{{chem2|RhCl(PPh3)3 + CS2 -> RhCl(CS2)(PPh3)3}} |
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:{{chem2|RhCl(CS2)(PPh3)3 -> RhCl(CS)(PPh3)2 + SPPh3}} |
:{{chem2|RhCl(CS2)(PPh3)3 -> RhCl(CS)(PPh3)2 + SPPh3}} |
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The reaction of {{chem2|(C5H5)2Ni2(CO)2}} with carbon disulfide gives ca 30% yield of {{chem2|(C5H5)3Ni3(CS)2}}, a trimetallic cluster with a triply bridging thiocarbonyl ligands. Many other complicated reactions have been reported. |
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A variety of other routes have been developed, including addition of sulfur reagents to [[metal carbyne complex]]es. |
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==Structure and bonding== |
==Structure and bonding== |
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Latest revision as of 14:18, 23 October 2025
A transition metal thiocarbonyl complex is a coordination compound containing the ligand CS. Whereas metal carbonyl complexes are very common, even industrially important, only a few dozen thiocarbonyl complexes are known.[1]
The main challenge for the preparation of thiocarbonyl complexes arises from the non-availability of carbon monosulfide. Thus, the CS ligand is often extruded from thiocarbonyl-containing precursors. One example involves thiophosgene, which reacts with disodium tetracarbonylferrate:
- Na2Fe(CO)4 + CSCl2 → Fe(CO)4CS + 2 NaCl
Instead of thiophosgene, chlorothioformates (ClC(S)OAr) have also been used as a source of CS ligand. The thiocarbonyl analogue of Vaska’s complex is prepared in this way.[2]
Carbon disulfide is another source of thiocarbonyl, albeit less electrophilic. It forms η2-CS2 complexes, which are susceptible to desulfurization:[3]
- RhCl(PPh3)3 + CS2 → RhCl(CS2)(PPh3)3
- RhCl(CS2)(PPh3)3 → RhCl(CS)(PPh3)2 + SPPh3
The reaction of (C5H5)2Ni2(CO)2 with carbon disulfide gives ca 30% yield of (C5H5)3Ni3(CS)2, a trimetallic cluster with a triply bridging thiocarbonyl ligands. Many other complicated reactions have been reported.
A variety of other routes have been developed, including addition of sulfur reagents to metal carbyne complexes.
Structure and bonding
[edit]
According to the Covalent bond classification method, terminal CS is classified as an L ligand, i.e., a charge-neutral Lewis base. With respect to HSAB theory, it is classified as soft. According to spectroscopic measurements, CS is a superior pi-acceptor relative to CO, as indicated by the shortness of M-CS vs M-CO bonds.[1]
CS also serves as bridging ligand.
Thiocarbonyl ligands undergo a variety of reactions often undergoing reduction to thioformyl or even methanethiolate.
Selenocarbonyl and tellurocarbonyl complexes
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Several complexes of CSe and CTe have been characterized.[5] The first examples were prepared from the osmium dichlorocarbene complex.[6]
- OsCl2(CCl2)(PPh3)2(CO) + 2 EH− → OsCl2(CE)(PPh3)2(CO) + 2 Cl− + H2E (E = Se, Te; Ph = C6H5)
- ^ a b Petz, W. (2008). “40 Years of Transition-Metal Thiocarbonyl Chemistry and the Related CSe and CTe Compounds”. Coordination Chemistry Reviews. 252 (15–17): 1689–1733. doi:10.1016/j.ccr.2007.12.011.
- ^ Hill, A. F.; Wilton-Ely, J. D. E. T. (2002). “Chlorothiocarbonyl-bis(triphenylphosphine)iridium(I) [IrCl(CS)(PPh3)2]”. Inorganic Syntheses. 33: 244–245. doi:10.1002/0471224502.ch4.
- ^ Baird, M. C.; Wilkinson, G. (1966). “Thiocarbonyl complexes of transition metals”. Chemical Communications (9): 267. doi:10.1039/C19660000267.
- ^ Huang, Yining; Uhm, Haewon L.; Gilson, Denis F. R.; Butler, Ian S. (1997). “Phosphorus-31 Chemical Shift Anisotropies in Solid, Octahedral Chromium(0) Triphenylphosphine Derivatives”. Inorganic Chemistry. 36 (3): 435–438. doi:10.1021/ic960816u.
- ^ Frogley, Benjamin J.; Hill, Anthony F.; Watson, Lachlan J. (2020). “Advances in Transition Metal Seleno- and Tellurocarbonyl Chemistry”. Chemistry – A European Journal. 26 (56): 12706–12716. doi:10.1002/chem.202001588. PMID 32356334.
- ^ Clark, George R.; Marsden, Karen; Roper, Warren R.; Wright, L. James (1980). “Carbonyl, Thiocarbonyl, Selenocarbonyl, and Tellurocarbonyl Complexes Derived from a Dichlorocarbene Complex of Osmium”. Journal of the American Chemical Society. 102 (3): 1206–1207. doi:10.1021/ja00523a070.
