- Bond formation and coupling between germyl and bridging germylene ligands in dinuclear palladium(I) complexes
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The dinuclear palladium(I) complexes [L-(Ar2HGe)Pd(μ-GeAr2)2Pd(GeHAr2)L] (Ar = Ph, p-Tol; L= PMe3, tBuNC) contain terminal germyl and bridging germylene ligands with the experimentally observed Ge...Ge bond lengths of 2.8263(4) ? (L = PMe3) and 2.928(1) ? (L = tBuNC), which are close to the longest Ge-Ge bond reported to date [2.714(1) ?]. Significant Ge...Ge interactions between the germylene and germyl ligands (PMe3 complexes > tBuNC complexes) are supported by DFT calculations, Wiberg bond indices (WBI), and natural bond orbital (NBO) analyses. Exchanging tBuNC for PMe3 ligands increases the Ge...Ge interaction, and simultaneously activates two Pd-Ge bonds. Adding the chelating diphosphine 1,2-bis(diethylphosphino)-ethane (depe) to the PMe3 complexes results in the intramolecular coupling of germyl and germylene ligands followed by extrusion of a digermane.
- Tanabe, Makoto,Omine, Shumpei,Ishikawa, Naoko,Osakada, Kohtaro,Hayashi, Yoshihiro,Kawauchi, Susumu
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supporting information
p. 2679 - 2683
(2015/03/04)
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- Structural, spectral, and electrochemical investigations of para-tolyl-substituted oligogermanes
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The synthesis of four new oligogermanes containing para-tolyl-substituents has been achieved via the hydrogermolysis reaction, including the digermane Tol3GeGePh3, the trigermanes Tol3GeGePh2GeTol3 and Tol3GeGeTol2GeTol3, and the tetragermane Tol3GeGePh2GePh2GeTol3 (Tol?=?p-CH3C6H4). These four oligogermanes have been structurally characterized and their structures have been compared with those of their per-phenyl-substituted analogs. The digermane Tol3GeGePh3 exhibits an unusually short Ge-Ge bond distance of 2.408(1)?A?. The four para-tolyl-substituted oligogermanes have also been characterized by UV/visible spectroscopy and cyclic voltammetry. The expected red shift in the absorbance maximum with increasing catenation was observed for this series of compounds. Their cyclic voltammograms each contain n?-?1 irreversible oxidation waves (n?=?the number of Ge atoms), which is atypical since oligogermanes generally exhibit only one irreversible oxidation wave regardless of the degree of catenation.
- Amadoruge, Monika L.,Short, Erin K.,Moore, Curtis,Rheingold, Arnold L.,Weinert, Charles S.
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p. 1813 - 1823
(2010/08/05)
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- Preparation and Some Reactions of Diarylgermylenedialkali Metals
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The reactions of diarylgermanes with alkali metals in HMPA/THF or THF were found to give the corresponding diarylgermylenedialkali metals in high yields.Diphenylgermylenedipotassium reacted with aryl halides or carbonyl compounds to give reduction products predominantly.With alkyl halides, diphenylgermylenedipotassium gave mainly substitution products.
- Mochida, Kunio,Matsushige, Naoki,Hamashima, Mari
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p. 1443 - 1447
(2007/10/02)
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