Germyl- and germylene-bridged complexes of Rh/Ir and subsequent chemistry of a bridging germylene group

A series of neutral and cationic germylene-bridged complexes and a neutral germyl(germylene) complex have been synthesized and characterized by NMR spectroscopy and X-ray crystallography. Reaction of 1 equiv of primary germanes, RGeH(3) (R = Ph, (t)Bu), with RhIr(CO)(3)(dppm)(2)] (1) at low-temperature yields RhIr(GeH(2)R)(H)(CO)(3)(dppm)(2)] (R = Ph (3) or (t)Bu (4)), the products of single Ge-H bond activation, which upon warming transform to the germylene-bridged dihydrides, RhIr(H)(2)(CO)(2)(μ-GeHR)(dppm)(2)] (R = Ph (5) or (t)Bu (6)) by activation of a second Ge-H bond accompanied by CO loss. Both classes of compounds have the diphosphines folded back in a "cradle-shaped" geometry. Although compound 5 reacts with additional phenylgermane at -40 °C to give a germylene-bridged/germyl product, RhIr(GeH(2)Ph)(H)(2)(CO)(2)(κ(1)-dppm)(μ-GeHPh)(μ-H)(dppm)] (7), warming results in decomposition. However, reaction of 5 with 1 equiv of diphenylgermane at ambient temperature results in a novel mixed bis(μ-germylene) complex, RhIr(CO)(2)(μ-GeHPh)(μ-GePh(2))(dppm)(2)] (8), containing both mono- and disubstituted germylene fragments. Reaction of 1 equiv of diphenylgermane with complex 1 produces a similar monogermylene-bridged product, RhIr(H)(2)(CO)(2)(μ-GePh(2))(dppm)(2)] (9), while reaction of 1 with 2 equiv of diphenylgermane yields the germyl/germylene product RhIr(H)(GeHPh(2))(CO)(3)(κ(1)-dppm)(μ-GePh(2))(dppm)] (10). The above reactions, incorporating first one and then a second equivalent of primary and secondary germanes, were studied by low-temperature multinuclear NMR spectroscopy, revealing details about the stepwise activations of multiple Ge-H bonds. Reaction of diphenylgermane with the cationic complex RhIr(CH(3))(CO)(2)(dppm)(2)]CF(3)SO(3)] (2) leads to a cationic A-frame-type germylene- and hydride-bridged product, RhIr(CO)(2)(μ-H)(μ-GePh(2))(dppm)(2)]CF(3)SO(3)] (3), which reversibly activates H(2), yielding a germyl-bridged dihydride and reacts stoichiometrically with water, methanol, and HCl to yield the respective germanol, germamethoxy, and germylchloride products.