Germyl- and Germylene-Bridged Complexes of Rh/Ir and Subsequent Chemistry of a Bridging Germylene Group
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https://figshare.com/articles/dataset/Germyl_and_Germylene_Bridged_Complexes_of_Rh_Ir_and_Subsequent_Chemistry_of_a_Bridging_Germylene_Group/2535784
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资源简介：
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, RGeH3 (R = Ph, tBu), with [RhIr(CO)3(dppm)2] (1) at low-temperature yields [RhIr(GeH2R)(H)(CO)3(dppm)2] (R = Ph (3)
or tBu (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 tBu (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(GeH2Ph)(H)2(CO)2(κ1-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-GePh2)(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-GePh2)(dppm)2] (9), while reaction of 1 with 2 equiv of diphenylgermane
yields the germyl/germylene product [RhIr(H)(GeHPh2)(CO)3(κ1-dppm)(μ-GePh2)(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(CH3)(CO)2(dppm)2][CF3SO3] (2) leads to a cationic A-frame-type germylene- and hydride-bridged
product, [RhIr(CO)2(μ-H)(μ-GePh2)(dppm)2][CF3SO3] (3), which reversibly
activates H2, yielding a germyl-bridged dihydride and reacts
stoichiometrically with water, methanol, and HCl to yield the respective
germanol, germamethoxy, and germylchloride products.
创建时间：
2016-02-21
