Reactivity of triosmium and triruthenium carbonyls with 2,2 '-diamino-1,1 '-binaphthalene. Synthesis of C- and N-metalated derivatives

摘要

The reaction of [Os-3(MeCN)(2)(CO)(10)] with 2,2'-diamino-1,1'-binaphthalene (H(2)binam) affords the coordinatively unsaturated trinuclear derivative [Os-3(mu-H)(mu(3)-eta(2)-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 I is somewhat relieved by a weak interaction of a naphthalene C=C double bond with an Os atom. Curiously, treatment of [Ru-3(MeCN)(2)(CO)(10)] with H(2)binam does not give the ruthenium analogue of 1. The stepwise treatment of [Ru-3(CO)(12)] with LiHbinam and [HOEt2][BF4] leads to [Ru-3(mu-H)(mu-eta(1)-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 [Ru-3(mu-H)(2)(mu(3)-eta(2)-binam-C,N)(mu-eta(2)-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 H(2)binam. [References: 82]