1675-58-7Relevant articles and documents
Mono- and dinuclear germapalladacycles obtained via the Ge-Ge bond forming reactions promoted by palladium complexes
Tanabe, Makoto,Ishikawa, Naoko,Hanzawa, Masaya,Osakada, Kohtaro
, p. 5152 - 5158 (2008)
Heating a toluene solution of bis(germyl)palladium complex [Pd(GeHPh 2)2(dmpe)] (2) (dmpe = 1,2-bis(dimethylphosphino)ethane) at 70 °C produced a mixture of dipalladium complexes, one with bridging digermene and germylene ligands, [{Pd(dmpe)}2(μ-GePh 2)(μ-Ge2Ph4)] (3), and also a mononuclear tetragermapalladacyclopentane, [Pd(GePh2GePh2GePh 2GePh2)(dmpe)] (4), in 92:8 molar ratio, respectively. The reaction of H2GePh2 with 2 in 10:1 molar ratio formed complex 4 as the main product (3:4 = 4:96). Complexes 3 and 4 were isolated from the above reactions and characterized by X-ray crystallography and NMR spectroscopy. Complex 3 reacted with H2GePh2 (Pd:Ge = 1:10) at 80 °C to yield 4 quantitatively, whereas simple heating of 3 at the same temperature did not form 4 at all. Reaction pathways for the Ge-Ge bond formation are discussed.
Selective Synthesis and Derivatization of Germasilicon Hydrides
Stueger, Harald,Christopoulos, Viktor,Temmel, Andrea,Haas, Michael,Fischer, Roland,Torvisco, Ana,Wunnicke, Odo,Traut, Stephan,Martens, Susanne
, p. 4034 - 4038 (2016)
Mixed Si/Ge hydrides SixGeyHz are valuable precursors for the deposition of binary Si-Ge alloys. This work describes the synthesis and full characterization of the previously unknown germaisotetrasilane Ph3GeSi(SiH3)3 (2) on a multigram scale from the reaction of the lithium silanide LiSi(SiH3)3 with Ph3GeCl. The stability of the Si-Ge bond in 2 versus electrophiles and nucleophiles has been investigated with the primary aim of developing new approaches to mixed sila-H-germanes (H3Ge)xSi(SiH3)4-x. With 1 equiv of MeLi, 2 reacted cleanly under cleavage of one Si-Si bond to give Ph3GeSi(SiH3)2Li, which is a valuable synthon for further derivatization. In contrast, the dephenylation reaction of 2 with 1 or 2 equiv of CF3SO3H/iBu2AlH proceeded much less selectively and afforded the desired Ph/H-germasilanes Ph2HGeSi(SiH3)3 and PhH2GeSi(SiH3)3 along with considerable amounts of Si-Ge scission products.
Chromium carbonyl complexes with aryl mono- and oligogermanes: Ability for haptotropic rearrangement
Zaitsev, Kirill V.,Gloriozov, Igor P.,Oprunenko, Yuri F.,Lermontova, Elmira Kh,Churakov, Andrei V.
, p. 217 - 227 (2019/10/16)
The intra- and intermolecular inter-ring η6 ? η6-haptotropic rearrangements (IRHR), occurring by involving interactions to Ge atoms in arylgermanes, were investigated theoretically and experimentally. The new methods for the synthesis of non-symmetrical polyaromatic Ge compounds were elaborated. Digermane Ph3GeGeMe2Cl (2) was obtained from Ph3GeGeMe2NMe2 (1) under action of Me3SiCl. Aryl digermane Ph3GeGeMe2(η6-C6H5)Cr(CO)3 (4) was obtained after lithiation of (η6-C6H6)Cr(CO)3 (3) with subsequent interaction with 2. It was established that thermally induced intramolecular IRHR in 4 is not observed experimentally; at similar reaction conditions in the presence of tetralin C10H12 (7) the bimolecular intermolecular IRHR occurs giving (η6-C10H12)Cr(CO)3 (8). DFT analysis of the intramolecular IRHRs for model germane (p-Tol)2Ge(H)(η6-Tol-p)Cr(CO)3 (MC1) and digermane Ph3GeGeH2(η6-C6H5)Cr(CO)3 (MC2) indicates a plausible effect of 3c-2e (agostic) Ge–H···Cr interaction on success of such rearrangement. The theoretical activation barrier is determined to be in the range of 35–37 kcal/mol. The model compound (η6-C6H3(GeHPh2)Me2-p)Cr(CO)3 (12) was obtained from (η6-C6H4Me2-p)Cr(CO)3 (11). The decomposition of 12 was observed under conditions of thermally induced IRHR. Molecular structures of 8, 11 and 12 in a crystal were investigated by XRD.