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• W2094759872 abstract "In extension of previous studies with pentamethylcyclopentadienyl (Cp★, η5-C5Me5) vanadium complexes, decarbonylations in the presence of elemental chalcogens of the halfsandwich compounds CP(′)V(CO)4 and CP(′)V(CO)3L (L  SMe2, MeCN) containing either the unsubstituted cyclopentadienyl (Cp, η5-C5H5) or the monomethyl-substituted (Cp′, η5-C5H4Me) cyclopentadienyl ring ligand have been investigated. (The notation Cp(′) indicates that both the unsubstituted (Cp) and the monomethyl-substituted (Cp′) cyclopentadienyl complexes were used.) The main products obtained from CP(′)V(CO)3L and an excess of chalcogen were binuclear pentachalcogenides CP(′2V2E5 (bd1) (E  S, Se) and oxo-tritellurides Cp(′)2V2E3O (bd4) (E  Te), respectively. Oxygen-containing side-products such as Cp★2V2E3O (E  S, Se), CP′2V2S4O and Cp′VO(S5 were isolated from the reactions starting from CP′V(CO)4. Chalcogen abstraction from 1 by use of one equivalent of tri(n-butyl)phosphane (PnBU3) gave the tetrachalcogenides Cp(′)2V2E4 (2), while further addition of PnBu3 gave pseudocubane clusters Cp(′)4V4E4 (7) (E  S, Se). Small amounts of trisulfides CP(′)2V2S3 (3) were observed by 51V NMR spectroscopy in solutions of 1 and 2 in the presence of PnBu3. Binuclear tetracarbonyl-dichalcogenides Cp(′)2V2(CO)4E2 (6) (E  S, Te) were made by treating solutions of CP(′)V(CO)3(SMe2) with H2S and by photolysing CP(′)V(CO)4 in the presence of either H2S or TePn Bu3. The reactions Of Cp′2V2(CO)4S2 (6a′) with an excess of an oligochalcogenide Na2E5 (E  Se, Te) gave the mixed-chalcogenide complexes Cp2V2E2S2 (E  Se (2d′) and Te (2f′)), which react with two equivalents of PnBu3 or NiCp2 to the pseudocubane cluster Cp′4V4S4 (7a′). Thermal decarbonylation of the tetracarbonyl-dichalcogenides Cp(′)2V2(CO)4E2 (6) in toluene solution gave the tetranuclear clusters Cp(′)4V4E4 (7) (E  S, Te) directly. The analogous pentamethylcyclopentadienyl compounds Cp★4V4E4 (7★) (E  S, Te) were also prepared. The spectroscopic data for the new CpV and Cp′V complexes are compared with those of the corresponding Cp★V compounds." @default.
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• W2094759872 date "1992-06-01" @default.
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• W2094759872 title "Cyclopentadienyl- and methylcyclopentadienyl-vanadium complexes containing chalcogen bridges: dechalcogenation to pseudocubane clusters" @default.
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• W2094759872 doi "https://doi.org/10.1016/0022-328x(92)80096-g" @default.
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