| Abstract | Acid hydrolysis of [Ru5(CO)15(μ4-PNiPr2)] (2) or protonation of the anionic PO cluster [Ru5(CO)15(μ4-PO)]- (3) affords the hydroxyphosphinidene complex [Ru5(CO)15(μ4-POH)]·1·[H2NiPr2][CF3SO3], which cocrystallizes with a hydrogen-bonded ammonium triflate salt. Reaction of [Ru5(CO)15(μ4-PNiPr2)] (2) with bis(diphenylphosphino)methane (dppm) leads to [Ru5(CO)13(μ-dppm)(μ4-PNiPr2)] (4). Acid hydrolysis of 4 leads to the dppm-substituted hydroxyphosphinidene [Ru5(CO)13(μ-dppm)(μ4-POH)] (5), which is analogous to 1, but unlike 1, can be readily isolated as the free hydroxyphosphinidene acid. Compound 5 can also be formed by reaction of 3 with dppm and acid. The cationic hydride cluster [Ru5(CO)13(μ-dppm)(μ3-H)(μ4-POH)][CF3SO3] (6) can be isolated from the same reaction if chromatography is not used. Compound 4 also reacts with HBF4 to form the fluorophosphinidene cluster [Ru5(CO)13(μ-dppm)(μ4-PF)] (7), while reaction with HCl leads to the μ-chloro, μ5-phosphide cluster [Ru5(CO)13(μ-dppm)(μ-Cl)(μ5-P)] (8). |
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