Stepwise conversion of [Os(CF3CO2)2(CO)4] into [Os(pyS)2(CO)2]: X-ray crystal structures of the complexes [Os(pyS)2(CO) x ] where x= 2 or 3 and pyS is the pyridine-2-thionato ligand
| Autor: | Antony J. Deeming, Kenneth I. Hardcastle, Neil P. Randle, M. Nafees Meah |
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| Rok vydání: | 1989 |
| Předmět: | |
| Zdroj: | Journal of the Chemical Society, Dalton Transactions. :2211 |
| ISSN: | 1364-5447 0300-9246 |
| Popis: | The tetracarbonyl osmium(II) complex [Os(CF3CO2)2(CO)4] or its decarbonylated derivative [Os(CF3-CO2)2(CO)3] reacts with pyridine-2-thione (pySH) in refluxing chloroform by substitution and addition respectively to give the compound fac-[Os(CF3CO2)2(pySH)(CO)3] containing monodentate trifluoroacetate ligands and S-bonded pySH. This complex spontaneously eliminates trifluoroacetic acid in the same refluxing solvent to give fac-[Os(CF3CO2)(pyS)(CO)3] which has bidentate pyS and monodentate trifluoroacetate. The same reagents in refluxing toluene give [Os(pyS)2(CO)3] but no further decarbonylation occurs unless this tricarbonyl complex is treated with Me3NO at room temperature and then [Os(pyS)2(CO)2] is formed. The single-crystal X-ray structures of the complexes [Os(pyS)2(CO)3] and [Os(pyS)2(CO)2] have been determined; the former contains non-interconverting monodentate and bidentate pyS but both ligands are chelating in the latter. Four intermediates in the overall conversion of [Os(CF3CO2)2(CO)4] into [Os(pyS)2(CO)2] are identified. This complex may also be synthesised by the direct reaction of pyridine-2-thione with [Os3(CO)12]. |
| Databáze: | OpenAIRE |
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