Reactions of the clusters [Os3(CO)10(MeCN)2)] and [Ru3(CO)12] with (2-aminophenyl)phosphine P(2-NH2C6H4)H2.: A comparison of the reactivity of amino and phosphino groups with clusters

Article abstract of DOI:10.1016/S0020-1693(02)01259-8

The reaction of (2-aminophenyl)phosphine P(2-NH₂C₆H₄)H₂ with [Os₃(CO)₁₀(MeCN)₂] gives the compounds [Os₃(CO)₁₁{P(2-NH₂C₆H ₄)H₂}] (1), [1,2-Os₃(CO)₁₀{P(2-NH₂C₆H ₄)H₂}₂] (2) and [Os₃(μ-H)(CO)₁₀{μ-P(2-NH₂C ₆H₄)H}] (3). Thermolysis of compounds 1 and 3 in cyclohexane affords in quantitative yields [Os₃(μ-H)₂(CO)₉{μ₃-P (2-NH₂C₆H₄)}] (4). However, the direct reaction of P(2-NH₂C₆H₄)H₂ with [Ru₃(CO)₁₂] yields only the nonacarbonyl species [Ru₃(μ-H)₂(CO)₉{μ₃-P (2-NH₂C₆H₄)}] (5). The phosphino group coordinates more favorably than the amino group and P-H bond activation is favored over amino coordination.