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

The reaction of (2-aminophenyl)phosphine P(2-NH2C6H4)H-2 with [Os-3(CO)(10)(MeCN)(2)] gives the compounds [Os-3(CO)(11){P(2-NH2C6H4)H-2}] (1), [1,2-Os-3(CO)(10){P(2-NH2C6H4)H-2}(2)] (2) and [Os-3(mu-H)(CO)(10){mu-P(2-NH2C6H4)H)] (3). Thermolysis of compounds 1 and 3 in cyclohexane affords in quantitative yields [Os-3(mu-H)(2)(CO)(9){mu(3)-P(2-NH2C6H4)}] (4). However, the direct reaction of P(2-NH2C6H4)H-2 with [Ru-3(CO)(12)] yields only the nonacarbonyl species [Ru-3(mu-H)(2)(CO)(9){mu(3)-P(2-NH2C6H4)}] (5). The phosphino group coordinates more favorably than the amino group and P-H bond activation is favored over amino coordination. (C) 2002 Elsevier Science B.V. All rights reserved.