Reactivity of Triosmium and Triruthenium Carbonyls with 2,2‘-Diamino-1,1‘-binaphthalene. Synthesis of C<i>-</i> and N<i>-</i>Metalated Derivatives

The reaction of [Os3(MeCN)2(CO)10] with 2,2‘-diamino-1,1‘-binaphthalene (H2binam) affords the coordinatively unsaturated trinuclear derivative [Os3(μ-H)(μ3-η2-Hbinam-N,C)(CO)9] (1), which contains a C-metalated Hbinam ligand attached to an Os atom through an NH2 group and to the remaining two Os atoms through the metalated C atom. The unsaturation of 1 is somewhat relieved by a weak interaction of a naphthalene CC double bond with an Os atom. Curiously, treatment of [Ru3(MeCN)2(CO)10] with H2binam does not give the ruthenium analogue of 1. The stepwise treatment of [Ru3(CO)12] with LiHbinam and [HOEt2][BF4] leads to [Ru3(μ-H)(μ-η1-Hbinam-N)(CO)10] (2), in which an N-metalated Hbinam acts as an edge-bridging amido ligand. Complex 2 reacts with bis(diphenylphosphanyl)methane (dppm) to give [Ru3(μ-H)2(μ3-η2-binam-C,N)(μ-η2-dppm-P,P)(CO)7] (3). This complex contains a doubly C- and N-metalated binam ligand attached to a Ru atom through the metalated C atom and to the remaining two Ru atoms through the metalated NH fragment. Compounds 1 and 3 are the first examples of C-metalated derivatives of H2binam.