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

Inorganic Chemistry, ISSN: 0020-1669, Vol: 51, Issue: 7, Page: 4020-4034
2012
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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 (R = Ph, Bu), with [RhIr(CO) (dppm) ] (1) at low-temperature yields [RhIr(GeH R)(H)(CO) (dppm) ] (R = Ph (3) or Bu (4)), the products of single Ge-H bond activation, which upon warming transform to the germylene-bridged dihydrides, [RhIr(H) (CO) (μ-GeHR) (dppm) ] (R = Ph (5) or 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 Ph)(H) (CO) (κ -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) (μ-GeHPh)(μ-GePh )(dppm) ] (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) (CO) (μ-GePh )(dppm) ] (9), while reaction of 1 with 2 equiv of diphenylgermane yields the germyl/germylene product [RhIr(H)(GeHPh )(CO) (κ -dppm)(μ- GePh )(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 )(CO) (dppm) ][CF SO ] (2) leads to a cationic A-frame-type germylene- and hydride-bridged product, [RhIr(CO) (μ-H)(μ- GePh )(dppm) ][CF SO ] (3), which reversibly activates H , yielding a germyl-bridged dihydride and reacts stoichiometrically with water, methanol, and HCl to yield the respective germanol, germamethoxy, and germylchloride products. © 2012 American Chemical Society.

Bibliographic Details

Mobarok, Md Hosnay; McDonald, Robert; Ferguson, Michael J; Cowie, Martin

American Chemical Society (ACS)

Chemistry

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