37044-16-9Relevant academic research and scientific papers
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.
Structural, spectral, and electrochemical investigations of para-tolyl-substituted oligogermanes
Amadoruge, Monika L.,Short, Erin K.,Moore, Curtis,Rheingold, Arnold L.,Weinert, Charles S.
, p. 1813 - 1823 (2010/08/05)
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.
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 XVI. SYNTHESE α,ω-DICHLORIERTER POLYGERMANE Cl(Ph2Ge)nCl (n = 2,3,4) DURCH GERMYLEN-EINSCHUB
Haeberle, Karl,Draeger, Martin
, p. 155 - 166 (2007/10/02)
The germylene Ph2Ge of Ph2GeHCl and NEt3 inserts in excess Ph2GeHCl and forms polygermanes Cl(Ph2Ge)nH.This one-pot reaction and subsequent chlorination to Cl(Ph2Ge)nCl has been optimized.Increasing amounts of NEt3 step up the yields of higher polygerm
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
SYNTHESE DE COMPOSES A LIAISON MIVB-MERCURE. PRECURSEURS D'ESPECES MONOVALENTES (GERMYNES), ET BIVALENTES (GERMYLENES), DE RADICAUX CENTROMETALLES ET D'INTERMEDIAIRES
Riviere, P.,Castel, A.,Satge, J.
, p. 351 - 367 (2007/10/02)
Polynuclear germyl-mercury compounds are obtained from the reaction of organohydrogermanes PhnGeH4-n or digermanes Ph2nGe2H4-n (n = 1, 2) with dialkylmercury R2Hg.Di- or tri-mercurated geminal polygermates thus synthesized generally present a low stability and undergo thermal- or photodecompositions leading to the corresponding monovalent (germynes), divalent (germylenes) or, trivalent (germanium centered radicals) species and also to intermediate biradicals which could be considered as limit forms of germanium doubly-bonded compounds .Such intermediates have been chemically and spectroscopically characterized.Extension of these reactions to the silicon analogs met with difficulties, and thus previously observed differences between silicon and germanium chemistry were confirmed.
