- METHOD FOR PRODUCING 14 GROUP METAL LITHIUM COMPOUND
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PROBLEM TO BE SOLVED: To provide a method for quantitatively producing a group 14 metal lithium compound under a mild condition. SOLUTION: The method for producing a group 14 metal lithium compound represented by formula (4): R4-nMLin comprises reacting a compound represented by formula (1): R4-nMXn and lithium in the presence of a polycyclic aromatic compound represented by formula (2) or formula (3). [In formula (1) and formula (2), R is a hydrocarbon group; M is a metal atom selected from Si, Ge and Sn; X is a halogen atom or R3M- (R and M are the same as mentioned above); and n is 1 or 2] and [R1 is H or a hydrocarbon group; and m is an integer of 0 to 5.] SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0072
(2016/10/31)
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- Stannyl-Lithium: A Facile and Efficient Synthesis Facilitating Further Applications
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We have developed a highly efficient, practical, polycyclic aromatic hydrocarbon (PAH)-catalyzed synthesis of stannyl lithium (Sn-Li), in which the tin resource (stannyl chloride or distannyl) is rapidly and quantitatively transformed into Sn-Li reagent at room temperature without formation of any (toxic) byproducts. The resulting Sn-Li reagent can be stored at ambient temperature for months and shows high reactivity toward various substrates, with quantitative atom efficiency.
- Wang, Dong-Yu,Wang, Chao,Uchiyama, Masanobu
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supporting information
p. 10488 - 10491
(2015/09/28)
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- Preferential carbene insertion into Ge-H vs. other heavier group 14 hydrides via samarium carbenoids
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The relative reactivities of Zn, Al, and Sm carbenoids in the chemoselective carbene insertion reaction of heavier group 14 hydrides were studied. By variation of the reaction protocols using Sm carbenoids, insertion reaction can favour the Ge-H bonds to give Ge-alkylated derivatives in good to high yield.
- Kondo, Hitoshi,Yamanoi, Yoshinori,Nishihara, Hiroshi
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p. 6671 - 6673
(2011/08/02)
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- Formation of silicon-carbon bonds by photochemical irradiation of (η5-C5H5)Fe(CO)2SiR3 and (η5-C5H5)Fe(CO)2Me to Obtain R3SiMe
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Photochemical irradiation of an equimolar mixture of (η5 -C5H5)Fe(CO)2SiR3, FpSiR 3, and FpMe leads to the efficient formation of the silicon-carbon-coupled product R3SiMe, R3 = Me 3, Me2Ph, MePh2, Ph3, ClMe 2, Cl2Me, Cl3, Me2Ar (Ar = C 6H4-p-X, X = F, OMe, CF3, NMe2). Similar chemistry occurs with related germyl and stannyl complexes at slower rates, Si > Ge Sn. Substitution of an aryl hydrogen to form FpSiMe2C6H4-p-X has little effect on the rate of the reaction, whereas progressive substitution of methyl groups on silicon by Cl slows the process. Also, changing FpMe to FpCH2SiMe3 dramatically slows the reaction as does the use of (η5-C 5Me5)Fe(CO)2 derivatives. A mechanism involving the initial formation of the 16e intermediate (η5-C 5H5)Fe(CO)Me followed by oxidative addition of the Fe-Si bond accounts for the experimental results obtained.
- Fortier, Skye,Zhang, Yongqiang,Sharma, Hemant K.,Pannell, Keith H.
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p. 1041 - 1044
(2010/04/25)
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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 and structural characterization of trimethylsilyl-substituted germylzinc halides, (Me3Si)3GeZnX (X = Cl, Br, and I) and silylzinc chloride, R(Me3Si)2SiZnCl (R = SiMe3 and Ph)
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The trimethylsilyl-substituted germylzinc halides, (Me3Si) 3GeZnX (X = Cl, Br, and I), and silylzinc chlorides, R(Me3Si)2SiZnCl (R = SiMe3 and Ph) have been prepared and their molecular structures have been full determined by spectroscopic and single-crystal X-ray diffraction methods. The germylzinc halides and silylzinc chlorides have dimeric structures consisting of two μ-halogen atoms. The reactivity of germylzinc chloride with substrates is also examined.
- Nanjo, Masato,Oda, Takashi,Mochida, Kunio
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p. 100 - 108
(2007/10/03)
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- Preparation and structural characterization of bis[tris(trimethylsilyl)-germyl]zinc, [(Me3Si)3Ge]2Zn
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Bis[tris(trimethylsilyl)germyl]zinc, [(Me3Si)3Ge]2Zn, was prepared by the reaction of [tris(trimethylsilyl)germyl]lithium, (Me3Si)3GeLi(thf), with zinc chloride, ZnCl2, and by the reaction of tris(trimethylsilyl)germane, (Me3Si)3GeH, with diethylzinc, Et2Zn. The molecular structure of [(Me3Si)3Ge]2Zn was determined by spectroscopic and X-ray diffraction methods. In [(Me3Si)3Ge]2Zn, the two tris(trimethylsilyl)germyl ligands, (Me3Si)3Ge, are bonded in a linear fashion to the zinc atom and are staggered with respect to each other. The reactions of bis(germyl)zinc with substrates were also examined.
- Nanjo, Masato,Oda, Takashi,Mochida, Kunio
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p. 1261 - 1264
(2007/10/03)
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- Preparation and characterization of tris(trimethylsilyl)germylzinc chloride and bis[tris(trimethylsilyl)germyl]zinc
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The molecular structure of (Me3Si)3GeZnCl (1) has been determined by single-crystal X-ray diffraction. The germylzinc chloride 1 has a dimeric structure consisting of two μ-Cl atoms. The compound 1 reacted with (Me3Si)3GeLi in diethyl ether to give [(Me3Si)3Ge]2Zn (2), quantitatively. The structure of bis(germyl)zinc 2 has been also elucidated by X-ray diffraction.
- Nanjo, Masato,Oda, Takashi,Mochida, Kunio
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p. 108 - 109
(2007/10/03)
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- Platinum-catalyzed bis-germylation of alkynes with organodigermanes and cyclic oligogermanes
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Hexamethyldigermane, Me3GeGeMe3, reacted with various alkynes in the presence of platinum complexes at 120 °C to afford Z-1,2-bis(germyl)ethenes in moderate to good yields. Terminal alkynes exhibit higher reactivities than internal ones. [Pt(acac)2] and [Pt(dba)2] serve as efficient catalysts, while [Pt(PPh3)4], [PtCl2(PPh3)2], and [Pt(dba)2]-phosphite were found to be inactive. Four- and six-membered cyclic oligogermanes, such as dodecamethylcyclohexagermane, (Me2Ge)6, reacted with alkynes in the presence of platinum catalysts to yield 1,4-digermacyclohexa-2,5-dienes in ca. 30% yield. The reactions of phenylacetylene with 1,2-digermacyclohexa-3,5-dienes afforded the corresponding 1,4-digermacycloocta-2,5,7-trienes in 93% yield. Bis(germyl)platinum complexes having various tertiary phosphine ligands have been prepared as models of a key intermediate in the above mentioned catalytic bis-germylation of alkynes, and their structures have been established by spectroscopic methods and X-ray crystallography. Bis(germyl)platinum complexes reacted with phenylacetylene to give the corresponding insertion products, germyl(germylvinyl)platinum species, whose structures have been determined by spectroscopic and X-ray analysis. Germyl(germylvinyl)platinum complexes were found to liberate a bis-germylation product of the alkyne upon heating. The result supports a mechanism involving the oxidative addition of a digermane to a Pt(0) complex, the insertion of an alkyne into one of the two Pt-Ge bonds to give a germyl(germylvinyl)platinum species, and the reductive elimination of the bis-germylation product of the alkyne. Evidence suggesting the extrusion of a germylene unit from the bis-germylplatinum species has been obtained, accounting for the generation courses of other by-products.
- Mochida, Kunio,Wada, Tohru,Suzuki, Kaoru,Hatanaka, Wakako,Nishiyama, Yuriko,Nanjo, Masato,Sekine, Akiko,Ohashi, Yuji,Sakamoto, Masato,Yamamoto, Akio
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p. 123 - 137
(2007/10/03)
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- Photochemistry of group 14 1,1,1-trimethyl-2,2,2-triphenyldimetallanes (Ph3MM′Me3; M, M′ = Si, Ge). Direct detection and characterization of silene and germene reactive intermediates
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The photochemistry of trimethylsilyltriphenylgermane (Ph3GeSiMe3), triphenylsilyltrimethylgermane (Ph3SiGeMe3), and 1,1,1-trimethyl-2,2,2-triphenyldigermane (Ph3GeGeMe3) has been studied in hydrocarbon solution by steady state and laser flash photolysis methods and is compared to previously reported data for the homologous disilane Ph3SiSiMe3. A variety of products are formed upon photolysis of the three compounds in the presence of 2,3-dimethyl-1,3-butadiene or chloroform, but in each case the major ones are derived from M-M′ bond homolysis and dimethyl- or diphenylgermylene extrusion. The trapping products of the 1,3,5-(1-metalla)hexatriene derivatives formed by [1,3]-MMe3 migration into the ortho-position of one of the phenyl rings are formed as well, in yields of 9-30%. While these experiments indicate that germylenes are formed in at least twice the yield of the 1,3,5-(1-metalla)hexatrienes, only the latter and triphenylsilyl or triphenylgermyl radicals can be detected by laser flash photolysis techniques. The metallaenes have been identified on the basis of their time-resolved UV absorption spectra and absolute rate constants for reaction with 2,3-dimethylbutadiene, methanol, acetone, acetic acid, oxygen, and carbon tetrachloride and can be distinguished from germylenes by their lack of reactivity toward triethylsilane and chloroform. Radical formation is shown to result from reaction of the triplet states of these compounds, and a triplet lifetime is estimated for Ph3GeSiMe3 and compared to that of the disilane homologue. The results of time-resolved experiments on other, related compounds are discussed in light of these results.
- Leigh, William J.,Toltl, Nicholas P.,Apodaca, Paula,Castruita, Madeli,Pannell, Keith H.
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p. 3232 - 3241
(2008/10/08)
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- A novel route to triphenylgermyl europium complexes. Crystal structure of(Ph3Ge)2Eu(DME)3
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(Ph3Ge)2Eu(THF)4 (1a) and (Ph3Ge)2Eu(DME)3 (1b) have been synthesized by reacting Ph3GeH with europium naphthalene, C10H8Eu(THF)2, in THF or DME, respectively. The reaction of Ph3GeH with C10H8[EuI(DME)2]2 in DME yielded Ph3GeEuI(DME)2 (2). The addition of two equivalents of CH3I to a solution of 1b in THF produced Ph3GeMe and EuI2(DME)2 with almost quantitative yields. Complex 2 easily disproportionates forming mixtures of 1b and EuI2(DME)2. The molecular structure of 1b was determined from X-ray diffraction data.
- Fedorova, Elena E.,Trifonov, Alexander A.,Bochkarev, Mikhail N.,Girgsdies, Frank,Schumann, Herbert
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p. 1818 - 1822
(2008/10/08)
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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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- METHYLPHENYLTRIPHENYLGERMYLSILANES FONCTIONNELS OPTIQUEMENT ACTIFS. II. REACTIONS DE CLIVAGE DE LA LIAISON Si-Ge
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The cleavage of a silicon-germanium bond in the presence of organometallics has been studied on the optically active compounds MePh(X)SiGePh3 (X=H, OMe).Depending on the nature of the nucleophile, we obtained mixed products, corresponding to the formation of Ph3Ge-, transient radical-anions, or catalytic reactions.
- Corriu, R. J. P.,Ould-Kada, S.,Lanneau, G. F.
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- Study of the insertion products of manganese in the silicon-hydrogen bond. Nature of the bond and proton exchange in the H-Mn-Si-H system
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NMR studies (29Si, 13C, and 1H) on silicon manganese hydrides slow the possibility of a bond interaction between silicon and hydrogen. Evidence is given for a slow intramolecular equilibrium (on the NMR time scale) between the silicon manganese hydride and the deinserted complex (silicon hydride and manganese moiety). In the latter, however, both moieties are associated and a strong ligand is needed to displace the silicon hydride. Chemical reactions show that protonation of the anion [(η5-CH3C5H4)Mn(CO) 2SiPh3]- leads only to the lateral hydride independent of its mode of generation. When the anion is alkylated, only the diagonal isomer is formed, showing that sterically crowded complexes prefer this geometry; thus the short distance observed between silicon and hydrogen does not seen to arise solely from steric hindrance.
- Colomer,Corriu,Marzin,Vioux
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p. 368 - 373
(2008/10/08)
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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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