37044-16-9Relevant articles and documents
Hydroalumination of Oligoalkynylgermanes and -digermanes – Reactions with Heterocumulenes by Al–C or Ge–C Bond Activation and Formation of a Hexazenedialuminum Complex
Uhl, Werner,Honacker, Christian,Lawrence, Neil,Hepp, Alexander,Schürmann, Lina,Layh, Marcus
, p. 945 - 955 (2018/09/21)
Hydroalumination of the dialkynylgermane Ph2Ge(C≡CtBu)2 (1) and the digermanes Phn(tBuC≡C)3–nGe–Ge(C≡CtBu)3–nPhn (2a: n = 2; 2b: n = 1) with two equivalents of H–AltBu2 or H–AlEt2 yielded the mixed Al/Ge compounds Ph2Ge[C(AltBu2)=CH-tBu]2 (3), [Ph2GeC(AltBu2)=CH-tBu]2 (4a), and [Ph2GeC(AlEt2)=CH-tBu]2 (4b). Reactions of 2b with both aluminum hydrides afforded inseparable mixtures of products. 3 reacted with heterocumulenes by retrohydroalumination. Phenyl isocyanate gave insertion of the C=N group into the resulting Ge–C(≡C–tBu) bond (5), whereas the NCS and NCN groups of phenyl isothiocyanate and a carbodiimide inserted into Al–Cvinyl bonds (6 and 7) with unaffected terminal Ge–C≡C–tBu moieties. The generation of 5 represents the first example of the insertion of a heterocumulene into a Ge–C bond, which may be favored by the activation of the isocyanate group by the Lewis acidic Al atom and the increased polarity of the N=C=O fragment as determined by NBO calculations. The reactions of the digermanes 4 with heterocumulenes were unselective and afforded inseparable mixtures. Treatment of 4a with the azide (4-tBu)C6H4CH2–N3 led interestingly to reductive coupling of two azide molecules, and the hexazene complex (tBuC6H4CH2N3–N3C6H4tBu)(AltBu2)2 (8) was isolated in moderate yield. Six nitrogen atoms form a dianionic chain, which coordinated two AltBu2 fragments by formation of two joint AlN4 heterocycles.
On Polygermanes, XVIII. Synthesis of the Multifunctional Digermanes Ph6-nGe2Cln (n = 2, 3, 4) and of Ph2GeCl2 under Pressure
Haeberle, Karl,Draeger, Martin
, p. 323 - 329 (2007/10/02)
Reaction of Ph6Ge2 with liquid HCl under pressure leads to di-, tri- and tetrachloro phenyldigermanes.The yield of higher chlorinated products increases with increasing pressure.The analogous reaction of Ph4Ge yields Ph2GeCl2 quantitatively.The Ge-Ge bond is most unstable in the case of Ph3Ge2Cl3 both chemically and thermally.The crystal structure of Ph2Ge2Cl4 has been determined (R = 0.057), Ge-Ge 241.3(1) pm. - Keywords: Functional Digermanes, Synthesis, Structure
UEBER POLYGERMANE XI. FUNKTIONALISIERUNG VON HEXAPHENYLDIGERMAN
Simon, Dietolf,Haeberle, Karl,Draeger, Martin
, p. 133 - 142 (2007/10/02)
The optimum conditions for selectively cleaving off two phenyl groups in Ge2Ph6 by trichloroacetic acid have been determined.Neither trihaloacetic acids nor HCl/AlCl3 nor reactive tetrahalides MCl4 are suitable reagents for cleaving one phenyl group alone
