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• 1074-29-9 trichlorophenylgermane 

Relevant academic research and scientific papers

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, 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-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-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.

The ground state energy levels and molecular structure of jet-cooled HGeCl and DGeCl from single vibronic level emission spectroscopy

Single vibronic level dispersed fluorescence spectra of jet-cooled HGeCland DGeCl have been recorded by laser excitation of selected bands of t he A A??1 - X A′1 electronic transition. Twenty-six ground state vibrational levels of HGeCl and 42 of DGeCl were measured, assigned,and fitted to standard anharmonicity expressions, which allowed all the harmonic frequencies to be determined for both isotopomers. A normal co ordinate least squares analysis obtained by fitting the harmonic frequencies yielded reliable values for five of the six force constants. The ground state effective rotational constants and force field data were combined to calculate average (rz) and approximate equilibrium (rez) structures, with rez (GeH) =1.586 (1) ?, rez (GeCl) =2.171 (2) ?, and the bond angle fixed at our CCSD(T)/aug-cc-pVTZ ab initio value of 93.9°. Comparisons show that the derived bond lengths are consistent with those of the appropriate diatomic molecules in their ground electronic states and the bond angle is similar to that of germylene (Ge H2). A Franck-Condon simulation of the vibrational intensities in the 000 band emission spectrum of HGeCl using ab initio force field data shows good agreement with experiment, lending credence to the vibrational analysis of the observed spectra.