Cyclopentadienyl dithiocarbamate and dithiophosphate molybdenum and tungsten complexes
Reactions of [MCp*Cl4] (M=Mo, W; Cp*=η5-C5Me5) with salts of the N,N-diethyldithiocarbamate [Et2dtc]− and O,O′-diethyldithiophosphate [Et2dtp]− anions yield the paramagnetic metal(V) complexes [MCp*Cl3(Et2dtc)] (M=Mo, W) and [MCp*Cl3(Et2dtp)] (M=Mo, W), respectively. Hydrolytic oxidation of both dit...
| Autores: | , , , , , , |
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| Tipo de recurso: | artículo |
| Fecha de publicación: | 1999 |
| País: | España |
| Institución: | Universidad de Alcalá (UAH) |
| Repositorio: | e_Buah Biblioteca Digital Universidad de Alcalá |
| Idioma: | inglés |
| OAI Identifier: | oai:ebuah.uah.es:10017/4245 |
| Acceso en línea: | http://hdl.handle.net/10017/4245 https://dx.doi.org/10.1016/S0022-328X(98)01222-4 |
| Access Level: | acceso abierto |
| Palabra clave: | Cyclopentadienyl Dithiocarbamate Dithiophosphate Molybdenum Tungsten Ciencia Química inorgánica Science Chemistry, inorganic |
| Sumario: | Reactions of [MCp*Cl4] (M=Mo, W; Cp*=η5-C5Me5) with salts of the N,N-diethyldithiocarbamate [Et2dtc]− and O,O′-diethyldithiophosphate [Et2dtp]− anions yield the paramagnetic metal(V) complexes [MCp*Cl3(Et2dtc)] (M=Mo, W) and [MCp*Cl3(Et2dtp)] (M=Mo, W), respectively. Hydrolytic oxidation of both dithiocarbamate–molybdenum complexes with aqueous hydrogen peroxide leads to η2-coordinated peroxo compounds [MoCp*Cl(O–O)O], which were also obtained from [MoCp*Cl4]. The related complexes [MCp′Cl(O–O)O] (M=Mo, Cp′=η5-C5H5; M=W, Cp′=η5-C5Me5) were isolated in a similar way. Reduction of a THF solution of [MoCp*Cl4] with one equivalent of 10% Na/Hg followed by the addition of one equivalent of ammonium dithiophosphate gives [MoCp*Cl2(Et2dtp)] which was also obtained via the reaction of [MoCp*Cl3(Et2dtp)] with MeMgCl, whereas reduction with three equivalents of Na/Hg in the presence of CNtBu leads to the molybdenum(II) complex [MoCp*(Et2dtp)(CNtBu)2] in high yield. All these compounds were characterized by elemental analysis, IR, 1H- and 13C-NMR spectroscopy, magnetic susceptibility measurements and the molecular structures of [Mo(η5-C5H5)Cl(O–O)O] and [Mo(η5–C5Me5)Cl3{η2-S2P(OEt)2}] were determined by X-ray diffraction studies. |
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