- Studies of germanium-platinum bonds in bis(aryl-substituted germyl)platinum complexes by laser flash photolysis and chemical trapping experiments
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The UV photolysis of bis(triaryl-substituted germyl)platinum complexes, Pt(Ar3Ge)2(PMe2Ph)2 (Ar = Ph, p-C6H4-SiMe3, and p-C6H 4C(CH3)3
- Mochida, Kunio,Masukawa, Yusuke,Yamada, Atsuko,Yanaga, Mai,Nanjo, Masato,Arii, Hidekazu,Gohdo, Masao,Wakasa, Masanobu
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- donor-acceptor oligogermanes: Synthesis, structure, and electronic properties
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A series of oligogermanes, (Me3Si)3GeGeCl 3, (C6F5)3GeGePh3, (C6F5)3GeGe(p-Tol)3, and (C 6F5)2Ge[Ge(p-Tol)3]2, containing substituents with different electronic properties at neighboring germanium atoms were synthesized. According to X-ray diffraction studies, UV/visible spectroscopy, and quantum chemical calculations, these donor-acceptor oligogermanes are characterized by energies of electronic transitions lower than those for other similar compounds.
- Zaitsev, Kirill V.,Kapranov, Andrey A.,Churakov, Andrei V.,Poleshchuk, Oleg Kh.,Oprunenko, Yuri F.,Tarasevich, Boris N.,Zaitseva, Galina S.,Karlov, Sergey S.
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p. 6500 - 6510
(2013/12/04)
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- Iron-catalyzed chlorination of silanes
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A simple and highly efficient iron-catalyzed method for the chlorination of silanes has been developed. By use of 0.5-2% of the Fe(III)-based catalyst FeCl3 or Fe(acac)3 in the presence of 1-1.5 equiv of acetyl chloride as the chlorine donor, a large number of silanes, alkoxysilanes, and silanols were converted to the corresponding chlorosilanes in 50-93% yields. In contrast to earlier reported methods often suffering from expensive catalysts or use of stoichiometric metal salts, hazardous reagents, and reaction conditions, the presently described methodology allows benign reaction conditions and simple workup while using only catalytic amounts of a readily available and economically viable iron catalyst.
- Savela, Risto,Zawartka, Wojciech,Leino, Reko
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p. 3199 - 3206
(2012/06/04)
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- Reaction of germanes and digermanes with triflic acid: The route to novel organooligogermanes
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Novel germanium containing triflates were prepared from the reactions of trifluoromethanesulfonic acid with tetraphenylgermane (1) and digermanes (Ph3GeGeMe3 (4), Ph3GeGePh3 (5)). The improved procedures for synthesis of known organogermanium compounds (Ph4Ge (1), Ph3GeCl (2), Ph3GeGeMe3 (4), Ph3GeGePh3 (5)) were also presented. The crystal structure of Ph3GeOTf (6) and Ph2Ge(OTf)Ge(OTf)Ph 2 (7) was studied by X-ray analysis. In 7 each germanium atom is pentacoordinated due to intramolecular interaction with O atom of the neighboring triflate group.
- Zaitsev, Kirill V.,Kapranov, Andrey A.,Oprunenko, Yuri F.,Churakov, Andrei V.,Howard, Judith A.K.,Tarasevich, Boris N.,Karlov, Sergey S.,Zaitseva, Galina S.
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p. 207 - 213
(2012/03/26)
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- Reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride
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The effect of substituents at the silicon and germanium atoms in reactions of organochlorosilanes with chloro-and organogermanes in the presence of aluminum chloride was studied. The only occurring process is the exchange of the chlorine atoms at Ge for the phenyl groups from Si; an increase in the number of methyl groups or chlorine atoms at Si promotes formation of phenyltrichlorogermane, and an increase in the number of phenyl groups or replacement of the chlorine atom at the Si atom by hydrogen leads to the formation of di-and triphenylchlorogermanes. Neither phenyl nor other radicals are transferred back from Ge to Si in the course of reactions of phenylgermanes with methylchlorosilanes in the presence of aluminum chloride; the only occurring processes are the exchange of the phenyl or methyl radicals bonded to Ge for the Cl atom bonded to Al and the disproportionation of phenylchlorogermanes. Nauka/Interperiodica 2006.
- Zhun,Sbitneva,Polivanov,Chernyshev
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p. 1564 - 1570
(2008/02/09)
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- Preparation, structural characterization, and photochemical reactions of silyl- and germylborates
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Silylborates (Li[PhnMe3-nSiBPh3], n = 1-3) and germylborates (Li[PhnMe3-nGeBPh3], n = 1-3; M[Et3- GeBPh3], M = Li, Na, K) were prepared by the reaction of the corresponding silyl- and germylalkali metals with triphenylborane in a hexane/benzene mixed solvent. The silyl- and germylborates were fully identified by 1H, 13C, 11B, and 7Li NMR spectroscopic methods. The solid-state structure of germylborates Li[Ph3GeBPh3] and M[Et3GeBPh 3] (M = Li and Na) were determined by X-ray diffraction analyses. The polymeric structure of M[Et3GeBPh3] was observed in the solid state and in hydrocarbon solution. The alkali metal atoms were located near the center of the benzene ring of triphenylborane and interacted with the neighboring borate molecules by Li+-π interaction. The polymeric structure was broken by the addition of MeOH. However, M[Et 3GeBPh3] was coordinated by three MeOH molecules to form a dimeric structure without methanolysis reaction. The primary processes in photochemical reactions of silyl- and germylborates were investigated by chemical trapping experiments and the CIDEP (chemical-induced dynamic electron polarization) method. The cleavage of the Ge-B (or Si-B) bonds of germylborates (or silylborates) was considered most probably to occur from their triplet states.
- Nanjo, Masato,Matsudo, Kazuhiko,Kurihara, Mari,Nakamura, Sayaka,Sakaguchi, Yoshio,Hayashi, Hisaharu,Mochida, Kunio
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p. 832 - 838
(2008/10/09)
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- Radical hydrometalation of functional ethylenic compounds: Radical autoinhibition changes the regioselectivity
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Hydrometalation of carbon-carbon double bonds by group 14 hydrides is inhibited by carbonyl compounds-mainly by α,β-unsaturated carbonyl groups-as efficiently as by classical radical trapping compounds, such as galvinoxyl and hydroquinone. This phenomenon
- El Kadib, Abdelkrim,Feddouli, Amal,Riviere, Pierre,Delpech, Fabien,Riviere-Baudet, Monique,Castel, Annie,Ahra, Mohamed,Hasnaoui, Aissa,Burgos, Francisco,Manriquez, Juan M.,Chavez, Ivone
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p. 446 - 454
(2008/10/09)
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- Reactivity of 2,6-diethyl-4,8-dimethyl-1,5-dioxo-s-hydrindacene towards radical, anionic and cationic germylation
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The synthesis and diastereoisomeric resolution of 2,6-diethyl-4,8-dimethyl- 1,5-dioxo-s-hydrindacene allowed the determination of the structure of the meso compound by X-ray diffractometry. The diastereoisomers were inactive towards radical germylation but reacted with acidic hydrogermanes or germylithium yielding α-germylated alcohols. By contrast, they were poorly reactive towards germylamines or SET reactions. This diketone acts as an efficient spin trap in radical hydrogermylation of alkenes.
- El Kadib,Castel,Delpech,Rivière,Rivière-Baudet,Gornitzka,Aguirre,Manriquez,Chavez,Abril
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p. 1256 - 1264
(2008/10/09)
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- Phenyltrichlorogermane synthesis by the reaction of chlorobenzene and the dichlorogermylene intermediate formed from elemental germanium and tetrachlorogermane
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Phenyltrichlorogermane was synthesized with high selectivity, 96%, from elemental germanium, tetrachlorogermane, and chlorobenzene using no catalyst, almost all germanium and tetrachlorogermane being converted. Dichlorogermylene was formed as a reaction intermediate by the reaction of germanium with tetrachlorogermane and inserted into the C-Cl bond of chlorobenzene to yield phenyltrichlorogermane.
- Okamoto, Masaki,Asano, Takuya,Suzuki, Eiichi
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p. 5583 - 5585
(2008/10/08)
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- Selective synthesis of chlorohydrogermanes from mono-, di-, and trihydrogermanes
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Treatment of hydrogermanes, R4-nGeHn (R = Hex, Et, Ph, n = 1-3), with 2 equiv of CuCl2 in ether at room temperature or in toluene under reflux led to selective replacement of an H-Ge bond with a Cl-Ge bond, giving the corresponding chlorohydrogermanes, R4-nGeHn-1Cl, selectively.
- Ohshita, Joji,Toyoshima, Yutaka,Iwata, Arihiro,Tang, Heqing,Kunai, Atsutaka
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p. 886 - 887
(2007/10/03)
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- Photochemical bond homolysis in a novel series of metal-metal bonded complexes Ru(E)(E′)(CO)2(iPr-DAB)
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Photochemistry of the complexes trans,cis-Ru(E)(E′)(CO)2(iPr-DAB) (E = Cl, SnPh3, PbPh3, Mn(CO)5, Re(CO)5, Me; E′ (depending on E) = SnPh3, PbPh3, GePh3, Mn(CO)5, Re(CO)5) was found to be strongly dependent on the combination and characters of the axial ligands E and E′. Except for Ru(Cl)(SnPh3)(CO)2(iPr-DAB) and Ru(Cl)(PbPh3)(CO)2(iPr-DAB) which are nearly unreactive, one of the Ru-E/E′ bonds is split homolytically upon irradiation into the lowest-energy absorption band of the complex. For Ru(SnPh3)2(CO)2(iPr-DAB), this reaction occurs from a thermally equilibrated 3σπ* excited state with a rate constant of 2.3 × 105 s-1 and a temperature-dependent quantum yield (Ea = 1450 cm-1). The unselective Ru-Ge (60%) and Ru-Sn (40%) bond homolysis of Ru(SnPh3)(GePh3)(CO)2-(iPr-DAB) follows the same mechanism. On the other hand, bond homolysis is much faster (?108 s-1) for complexes which contain Ru-Me, Ru-Mn or Ru-Re bonds. Bond homolysis in these species is highly selective, since only Ru-Me, Ru-Mn and Ru-Re bond splitting was observed for Ru(Me)(SnPh3)(CO)2(iPr-DAB), Ru(SnPh3)(Mn(CO)5)(CO)2(iPr-DAB) and Ru(SnPh3)(Re(CO)5)(CO)2(iPr-DAB), respectively. The photoproduced [Ru(E)(CO)2(iPr-DAB)]· radicals were detected by time resolved UV-Vis spectroscopy on a timescale 10 ns-100 μs. The [Ru(SnPh3)(CO)2(iPr-DAB)]· radical was also characterised by EPR in the form of its adduct with PPh3. Depending on the solvent used, they either dimerise or abstract a chlorine atom from the solvent to produce Ru(Cl)(E)(CO)2(iPr-DAB).
- Aarnts, Maxim P.,Stufkens, Derk J.,Vlcek Jr., Antonin
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- Microwave-assisted Lewis acid catalysis: Application to the synthesis of alkyl- or arylhalogermanes
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Under microwave irradiation, alkyl- or arylhalogermanes RnGeX4-n (R = Et, Bu, Ph; X = Cl, Br) are obtained by redistribution reactions of R4Ge with GeX4. These experimental conditions permit the synthesis of such compounds in good yield in a few minutes at atmospheric pressure. The direct Friedel-Crafts germylation of benzene and toluene by germanium tetrachloride also has been performed, but yields were low.
- Laurent, Régis,Laporterie, André,Dubac, Jacques,Berlan, Jacques
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p. 2493 - 2495
(2008/10/08)
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- Etude du transfert monoelectronique entre des germylanions et des piegeurs de spin dia et paramagnetiques
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Reactions between organogermyllithium R3GeLi and several substrates favoring SET reactions (3,5-di-t-butyl-orthoquinone, fluorenone, tetracyanoquinodimethane, 2,4,6-tri-t-butylnitrosobenzene, etc.) lead mainly to the formation of digermanes and O- or N-germyl adducts.All these reactions seem to proceed principally by single-electron transfer.An ESR study of the reaction shows transient organic radical anion formation and germanium-centred radicals R3Ge.The prepondancy of this mechanism can be demonstrated by the reaction between R3GeLi and a paramagnetic quinonic species, the galvinoxyl radical: the latter is almost completely transformed into a diamagnetic anion.Digermanes mainly produced in these reactions are formed via radicalar duplication as well as lithiogermolysis of reaction adducts.
- Riviere, P.,Castel, A.,Desor, D.,Abdennadher, C.
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- Triorganogermanium Selenocarboxylates: Synthesis and Reactions
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A series of triphenylgermanium selenocarboxylates 3 were synthesized and characterized.The esters 3 are thermally stable, but labile towards moisture and oxygen.They react with arenesulfenyl chlorides and areneselenenyl bromides at room temperature to afford the corresponding acyl arenesulfenyl selenides and acyl aryl diselenides in moderate yields. Keywords: Triorganogermanium Selenocarboxylates, Aroyl Aryl Diselenides, Aroyl Arenesulfenyl Selenides
- Kato, Shinzi,Ibi, Kazumasa,Kageyama, Hideki,Ishihara, Hideharu,Murai, Toshiaki
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p. 558 - 562
(2007/10/02)
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- Reactivity of dianionic hexacoordinate germanium complexes toward organometallic reagents. A new route to organogermanes
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Lithium and potassium tris(benzene-1,2-diolato)germanates (2a and 2b, respectively) and potassium tris(butane-2,3-diolato)germanate (3) are easily prepared from GeO2 in quantitative yields. They are very reactive toward organometallic reagents, the reactivity depending on the ligands on the germanium. Complexes 2 react with an excess of Grignard reagent to give the corresponding tetraorganogermanes R4Ge while the less reactive complex 3 leads to the functional triorganogermanes R3GeX. Tetraorganogermanes can also be prepared from complex 2b by reaction with organic bromides in the presence of Mg (Barbier reaction). The influence of Cp2TiCl2 and MgBr2 on the reactivity of Grignard reagents with these complexes was also investigated: in both cases formation of triorganogermanes was favored.
- Cerveau,Chuit,Corriu,Reyé
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p. 1510 - 1515
(2008/10/08)
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- Transition-Metal Silyl Complexes. 37.1 Reaction of Anionic Silyl, Germyl, and Stannyl Complexes [(η5-C5H4Me)(CO)2MnER 3]- (E = Si, Ge, Sn) with Geminal Organic Dihalides: A Novel Route for the Preparation of Carbene Complexes
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The anionic complexes Na[MeCp(CO)2MnER3] (E = Si, Ge, Sn) (MeCp = η5-C5H4Me), obtained by deprotonation of the corresponding hydrido complexes MeCp(CO)2Mn(H)ER3, react with 3,3-dichlorocyclopropenes to give the cyclopropenylidene complexes MeCp(CO)2Mn=C-CR=CR (2) by NaCl and R3ECl elimination. Aminocarbene complexes MeCp(CO)2Mn=C(NR2)R′ (5), including the N-methylpyridinylidene complex MeCp(CO)2Mn=CN(Me)CHCHCHCH (5h) and a thiazolinylidene derivative, MeCp(CO)2Mn=CN(Me)C(Me)CHS (5i), were alalogously prepared from [MeCp(CO)2MnSiMePh2]- and [R2N=C(R′)Cl]+. In these reactions, the anionic complexes Na[MeCp(CO)2MnER3] act as preparative equivalents to the dianionic complex MeCp(CO)2Mn2-. The X-ray structure analysis of 5i is reported (Mn-C(carbene) 197.0 (3) pm): monoclinic, space group P21/c (Z = 4), a = 736.4 (1) pm, b = 1418.4 (3) pm, c = 1304.6 (1) pm, β = 95.58 (1)°.
- Kirchg?ssner, Uwe,Piana, Hermann,Schubert, Ulrich
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p. 2228 - 2232
(2007/10/02)
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- Photochemical Reactions of Aryl-Substituted Digermanes through a Pair of Organogermyl Radicals
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The photochemical reactions of aryl-substituted digermanes were investigated by trapping experiments and a laser flash photolysis technique.The photolysis of phenylated digermanes resulted in germanium-germanium bond homolysis to give a pair of two germyl radicals.The germyl radicals abstracted a chlorine atom from carbon tetrachloride to give chlorogermanes.The pair of germyl radicals also underwent ipso-substitution, which was a precursor of the germylenes.The mechanism for the photochemistry of phenylated digermenes is discussed.
- Mochida, Kunio,Wakasa, Masanobu,Sakaguchi, Yoshio,Hayashi, Hisaharu
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p. 1889 - 1895
(2007/10/02)
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- Electrochemical Halogenation of Trisubstituted Germanes and Silanes
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Electrochemical halogenation of trisubstituted germanes and silanes in acetonitrile occured in the cathode compartment in contrast to the well-known electrochemical halogenations which always occur in the anode compartment.
- Okano, Mitsutoshi,Mochida, Kunio
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p. 1381 - 1382
(2007/10/02)
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- Etude de la reaction de germyllithiums sur la di-t-butyl-3,5 orthoquinone: mise en evidence d'un mecanisme par transfert monoelectronique
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Reactions between organogermyllithiums R3GeLi and 3,5-di-t-butylorthoquinone mainly give digermanes but also O-germylcatechol and germadioxolanes.It appears that these reactions start after an initial single electron transfer (SET) which is supported by a
- Riviere, P.,Castel, A.,Ko, Y. H.,Desor, D.
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p. 147 - 156
(2007/10/02)
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- Laser photolysis of aryl-substituted digermanes. Generation of germyl radicals and germylenes
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Laser flash photolysis of the phenyl-substituted digermanes (PhnMe3-nGe)2 results in Ge-Ge bond homolysis to give germyl radicals and probably a germylene.
- Mochida, Kunio,Wakasa, Masanobu,Nakadaira, Yasuhiro,Sakaguchi, Yoshio,Hayashi, Hisaharu
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p. 1869 - 1871
(2008/10/08)
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- Cycloaddition of Germylenes to 3,5-Di-t-butylorthoquinone
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The germylenes X2Ge, RGeX and R2Ge (X= halogen, OR; R= alkyl or aryl) react at room temperature with 3,5-di-t-butyl orthoquinone by regioselective cycloaddition.The corresponding substituted 2-germa-1,3-dioxolans are formed similarly in good yields, but t
- Riviere, Pierre,Castel, Annie,Satge, Jacques,Guyot, Daniel
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p. 157 - 164
(2007/10/02)
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- SYNTHESIS OF SOME TRIS(TRIMETHYLSILYL)GERMYL COMPOUNDS
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A variety of compounds containing the tris(trimethylsilyl)germyl group were prepared and characterized spectroscopically.Photolysis of adamantoyltris(trimethylsilyl)germane failed to yield the isomeric germene: in CCl4 the photolysis appeared to occur by a Norrish type 1 process.
- Brook, A. G.,Abdesaken, F.,Soellradl, H.
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- POLYGERMANES PRECURSEURS D'ESPECES DU GERMANIUM A COORDINNANCE NON USUELLE
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Several thermal or photochemical α-elimination reactions of functional polygermanes lead to germylenes, R2Ge.Photolysis of polygermanes, cyclopolygermanes and polygermylmercury compounds and also hydrogen abstraction from various organohydropolygermanes using t-BuO., lead to the formation of polymetallated chains containing one or two germanium-centered radicals.These polygermyl radicals give germylenes, R2Ge, germanium centered radicals Ge., α-digermyl diradicals (or digermenes) Ge.-Ge. or Ge=Ge> and β- or γ-polygermyl diradicals via ahomolytic monoelectronic α-elimination process.In some cases the formation of α-digermyl diradicals or digermenes can also be seen as occuring through dimerization of germylenes but with lower yields.All these intermediates have been characterized by several trapping reactions with dimethyl disulfide, 2,3-dimethylbutadiene or biacetyl.
- Riviere, P.,Castel, A.,Satge, J.,Guyot, D.
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p. 193 - 206
(2007/10/02)
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- OXIDATIVE-REDUCTIVE TRANSMETALLATION REACTIONS OF GERMYLMERCURY COMPOUNDS WITH BIS(ETHYLBENZENE)VANADIUM AND VANADOCENE
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The ionic complexHg>-+ has been obtained in the reaction of 2Hg with bis(ethylbenzene)vanadium.Dicyclopentadienylvanadium displaces mercury in 2Hg to give the covalent product Cp2VGe(C
- Bochkarev, M. N.,Pankratov, L. V.,Cherkasov, V. K.,Razuvaev, G. A.,Latyaeva, V. N.,Lineva, A. N.
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- THE CHEMICAL BEHAVIOUR OF COBALT-STABILIZED-CARBENES HAVING A TRISUBSTITUTED SILYL OR GERMYL LIGAND. STEREOSPECIFIC FORMATION OF BENZOYLSILANES FROM THE REACTION OF ORGANOSILYL-COBALT TETRACARBONYL DERIVATIVES WITH PHENYLLITHIUM
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We report the chemical behaviour of cobalt-stabilized carbenes, R3M(CO)3CoC(OEt)R', and their parent anions, R3M(CO)3CoC(O-)R', where M = Si or Ge.The anions where M = Si, R' = Ph decompose thermally into the corresponding benzoylsilanes; when the silicon atom is chiral (R3 = MePh-1-Np) optically active R3SiCOPh is obtained with complete retention of configuration.
- Cerveau, Genevieve,Colomer, Ernesto,Corriu, Robert J.P.,Young, J. Colin
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Brominations of triphenylallylsilane, methylphenyl-1-naphthylallylsilane, 2(1-naphthyl)-2-allyl-1,2,3,4-tetrahydro-2-silanaphthalene and triphenylallylgermane have been studied in carbon tetrachloride, acetic acid and methanol as solvents. Either cleavage
- Carre,Corriu,Henner
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p. 589 - 598
(2007/10/05)
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