112437-84-0Relevant academic research and scientific papers
Reactions of the unsaturated triosmium cluster [(μ-H)Os 3(CO)8(Ph2PCH2P(Ph)C 6H4)
Kabir, Shariff E.,Miah, Md. Arzu,Sarker, Nitai C.,Hossain, G.M. Golzar,Hardcastle, Kenneth I.,Rokhsana, Dalia,Rosenberg, Edward
, p. 3044 - 3053 (2005)
Treatment of the electronically unsaturated cluster [(μ-H)Os 3(CO)8(Ph2PCH2P(Ph)C 6H4)] (1) with HCl gas at ambient temperature in dichloromethane 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 an isomer of 2, 4. A similar reaction of 1 with HBr gas gave [(μ-H)Os 3(CO)8(μ-Br)(μ-dppm)] (5) as the only product which does not isomerize at 110 °C. In sharp contrast, treatment of 1 with HF gas gave 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)Os 3(CO)8(μ-η2-CH3CO 2)(μ-dppm)] (7). Structures of 2, 3, 4 and 6 were established crystallographically. In 2, both the chloride and the hydride ligands simultaneously bridge the same Os-Os edge and the dppm spans another Os-Os bond whereas in 4, all the three ligands bridge the same Os-Os edge. Compound 3 is comprised of an open Os3 arrangement in which one chloride bridges the open Os-Os edge, another chloride and a hydride mutually bridge an Os-Os bond and the third chloride is terminally coordinated to one of the Os atoms of the dppm bridged edge. The cation 6 consists of a triangle of osmium atoms in which the shortest Os-Os edge is bridged by a hydride and the metallated phenyl ring and the longest edge is bridged by another hydride and the diphosphine ligand.
