Methyl C_H activation of 2,4,5-trimethylthiazole by a triosmium cluster: X-ray structures of [(μ-H)Os3(CO)10?μ-η2-CH2C=NC(CH3)=C(CH3)S?] and [(μ-H)2Os3(CO)9?μ3-η2-CHC=C(CH3)SC(CH3)C=N?] (original) (raw)

Treatment of [Os3(CO)10(MeCN)2] with 2,4,5-trimethylthiazole at 25 °C leads to two new isomeric compounds [(μ-H)Os3(CO)10{μ-η2-CH2CNC(CH3)C(CH3)S}] (1) and [(μ-H)Os3(CO)10{μ-η2-CH2CC(CH3)SC(CH3)N}] (2) and the previously reported compounds [(μ-H)Os3(CO)10(μ-Cl)] (4) and [(μ-H)Os3(CO)10(μ-OH)] (5). Compounds 1 and 2, formed from activation of C-2 and C-4 methyl substituents of the ligand, respectively, undergo decarbonylation and further CH activation of the coordinated methylidene group at 110 °C to give [(μ-H)2Os3(CO)9{μ3-η2-CHCNC(CH3)C(CH3)S}] (6) and [(μ-H)2Os3(CO)9{μ3-η2-CHCC(CH3)SC(CH3)N}] (7). The compounds have been characterized by spectroscopic data together with single crystal X-ray diffraction studies for 1 and 7.[Os3(CO)10(MeCN)2] reacts at 25 °C with 2,4,5-trimethylthiazole to give two new isomeric compounds [(μ-H)Os3(CO)10{μ-η2-CH2CNC(CH3)C(CH3)S}] (1) and [(μ-H)Os3(CO)10{μ-η2-CH2CC(CH3)SC(CH3)N}] (2), and two known compounds [(μ-H)Os3(CO)10(μ-Cl)] (4) and [(μ-H)Os3(CO)10(μ-OH)] (5). Thermolysis of 1 and 2 at 110 °C gives [(μ-H)2Os3(CO)9{μ3-η2-CHCNC(CH3)C(CH3)S}] (6) and [(μ-H)2Os3(CO)9{μ3-η2-CHCC(CH3)SC(CH3)N}] (7), respectively. The compounds have been characterized by spectroscopic data together with single crystal X-ray diffraction studies for 1 and 7.

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