Reactions of the unsaturated triosmium cluster [(μ-H)Os3(CO)8(Ph2PCH2P(Ph)C6H4)] with HX (X = Cl, Br, F, CF3CO2,CH3CO2): X-ray structures of [(μ-H)Os3(CO)7(η1-Cl)(μ-Cl)2(μ-dppm)],[(μ-H)2Os3(CO)8(Ph2PCH2P(Ph)C6H4)]+[CF3O]− and the two isomers of

Treatment of the electronically unsaturated cluster [(μ-H)Os3(CO)8(Ph2PCH2P(Ph)C6H4)] (1) with HCl gas at ambient temperature afforded [(μ-H)Os3(CO)8(μ-Cl)(μ-dppm)] (2) and [(μ-H)Os3(CO)7(η1-Cl)(μ-Cl)2(μ-dppm)] (3). Thermolysis of 2 at 110 °C led to isomerization of 2 to 4. A similar reaction of 1 with HBr gas gave only [(μ-H)Os3(CO)8(μ-Br)(μ-dppm)] (5) which does not isomerizes at 110 °C. In sharp contrast, 1 reacts with HF gas to give the protonated species [(μ-H)2Os3(CO)8(Ph2PCH2P(Ph)C6H4)]+ (6). Treatment of 1 with CF3CO2H also gave cation 6 whereas CH3CO2H yielded [(μ-H)Os3(CO)8(μ-η2-CH3CO2)(μ-dppm)] (7).