Abstract
The aerobic oxidation of the binuclear ruthenium(0) carbonyl complexes [Ru2(CO)5(μ-dppm)2], dppm = Ph2PCH2PPh2, 1, and [Ru2(μ-H) (CO)5(μ-dppm)2]+X−, 2, has been studied. In acidic solution a 4-electron oxidation of 2 occurs to give [Ru2(μ-OH)2CO)4(μ-dppm)2]X2, X = ReO4 or BF4. However, in neutral solution aerobic oxidation occurs in 2-electron steps, with parallel 2-electron oxidation of a carbonyl ligand. The reaction of complex 1 in acetone solution gave a diruthenium(I) formate derivative [Ru2(μ-OH) (O2CH) (CO)3(μ-dppm)2], while reaction in dichloromethane solution gave a diruthenium(II) carbonate derivative [Ru2(CO3) (CO) (Cl) (μ-OH) (μ-CO) (μ-dppm)2]. The aerobic oxidation of 1 in the presence of methyl isocyanide and NH4[PF6] gave [Ru2(CO)2(CNMe)4(μ-dppm)2][PF6]2. The structural characterization of the products is described, and likely mechanisms of reaction are discussed.
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