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1.
The silanol TsiSiMe 2OH (Tsi = (Me 3Si) 3C) has been made by hydrolysis of the iodide TsiSiMe 2I in H 2O/dioxane or H 2O/Me 2SO. It has been shown to react with some acid chlorides RCOCl (R=Me, Et, CICH 2 Ph, 4-O 2NC 6H 4, and 3,5- (O 2N) 2C 6H 3) and anhydrides (RCO) 2O (R = Me, CF 3, or Ph) to give the carboxylates TsiSiMe 2OCOR, and with SO 2Cl 2 to give TsiSiMe 2OSO 2Cl. The triol TsiSi(OH) 3 has been made by treatment of TsiSiH(OH)I with H 2O/Me 2SO at 150°C or with a mixture of aqueous AgClO 4 and an organic solvent. The triol has been shown to react with RCOCl (R = Me, Et, or Ph) or (RCO) 2O (R = Ph) to give the corresponding TsiSi(OCOR) 3, with (CF 3CO) 2O to give TsiSi(OH) 2(OCOCF 3), and with a mixture of Me 3SiCl and AgClO 4 in benzene or one of Me 3Sil and (Me 3Si)NH to give TsiSi(OSiMe 3) 3. The triol is unusually stable, but decomposes at its m.p. of 285–290°C. 相似文献
2.
四甲基双硅桥联环戊二烯基钠与无水三氯化稀土在THF溶剂中反应合成了标题配合物Me 4Si 2(C 5H 4) 2LnCl[Ln:3Nd,4Sm,5Gd,6Y]和配合物Me 4Si 2(C 5H 4):Ln(C 5H 5)(THF)n[Ln:1La,n=1;2Pr,n=0].通过元素分析、 1HNMR、13CNMR和MS确证了配合物的结构,在THF溶液中重结晶获得配合物4的单晶,x射线衍射证明晶体结构为二聚体,4为单斜晶系,空间群为P2 1/c,晶体学数据a=1.2982(3)nm,b=1.2269(3)nm,c=1.3681(2)nm,β=96.79(2)°,V=2.162(1)nm 3,Z=2,D x=1.53g/cm 3,偏差因子R=0.068. 相似文献
3.
The UV photolysis (λ = 185 nm) of liquid methanol yields hydrogen, glycol, formaldehyde, methane and traces of ethane in quantum yields of 0·83, 0·78, 0·058, 0·05 and 0·002 resp. (related to φ(H 2) = 0·4 of the ethanol-actinometer (5 mole/1 in water)). The isotopic distribution of the hydrogen (85% HD) formed in the photolysis of CH 3OD shows, that as in the gasphase 2 the scission of the O---H-bond (1) is the major process. CH 3OH + h v (λ = 185 nm) → CH 3O • + H • (1) In methanoi-water mixtures (nearly all the light of the wavelength λ = 185 nm is absorbed by methanol) the quantum yields of hydrogen, glycol, methane and ethane are greatly reduced, while the formaldehyde yield remains unaffected. In 1 molar solution φ(H2) = 0·42, φ(glycol) = 0·32 and φ(CH4) = 6 x 10−4 is obtained. Ethane cannot be detected. 相似文献
4.
The new organosilicon bromides (Me 3Si) 2(ZMe 2Si)CSiMe 2Br with Z=PhO or MeS have been prepared and new spectroscopic data obtained for the previously reported compounds with Z=H, F, Br, Me, Ph, MeO or PhS. Competitions between pairs of bromides for a deficiency of AgBF 4 in Et 2O, with the determination of the ratio of the fluoride products by 19F-NMR spectroscopy, have led to the following approximate relative reactivities of the bromides and so to the relative abilities of the γ-Z groups to provide anchimeric assistance to the leaving of Br − in this reaction: Me, 1; Ph, 40; PhO, 3400; PhS, 5000; MeS, 7000; MeO, 54 000. In methanolysis in CH 2Cl 2, (Me 3Si) 2(MeOMe 2Si)CSiMe 2Cl has been found to be roughly 120 times as reactive as (Me 3Si) 2(PhOMe 2Si)CSiMe 2Cl. Combination of the results with previously available information suggests the following approximate order of ability of γ-groups Z to provide anchimeric assistance in reactions at the Si---X bonds in compounds (Me 3Si) 2(ZMe 2Si)CSiMe 2X: OCOMe>OMe>OCOCF 3>MeS>PhS, PhO>N 3, Cl>NCS>Ph>CH=CH 2>Me. 相似文献
5.
Reactions of mixtures of Cl 2MeSiSiMeCl 2 (1) and Me 2MCl 2 (M=Si, Ge, Sn) with either H 2S/NEt 3 or Li 2E (E=Se, Te) yielded the bicyclo[3.3.0]octanes Me 2M(E) 2Si 2Me 2(E) 2MMe 2. A carbon containing analog, (CH 2) 5C(S) 2Si 2Me 2(S) 2C(CH 2) 5, was prepared from 1 and (CH 2) 5C(SH) 2. Crystal structures of three of these compounds were determined and the observed conformations of the bicyclo[3.3.0]octane skeletons compared with results of density functional theory calculations. Another class of silchalcogenides featuring a bicyclo[3.3.0]octane skeleton, E(Me 2Si) 2Si 2Me 2(SiMe 2) 2E, was formed from the doubly branched hexasilane (ClMe 2Si) 2Si 2Me 2(SiMe 2Cl) 2 and H 2S/NEt 3 or Li 2E. All products were characterized by multinuclear NMR ( 1H, 13C, 29Si, 77Se, 119Sn, and 125Te). 相似文献
6.
The thermally (decomp. temp. 300°C) and completely air stable, novel coordination polymers [(Me 3Sn IV) 2(Me 3Sb V)M II(CN) 6] ∞ with M = Fe and Ru can be prepared by co-precipitation from aqueous solutions of Me 3SnCl, Me 3SbBr 2 and K 4[(M(CN) 6], or, alternatively, by the ion-exchange-like reaction of the polymers [A(Me 3Sn) 3M(CN) 6] ∞ (A + = Et 4N +, Cp 2Co +, Me 3Sn + etc.) with Me 3SbBr 2. IR-spectroscopic findings suggest a statistical distribution of quasi-octahedral M(CN-Sn··) 6-x(CNSb ··) x building blocks (with x = 0–6) within a three-dimensional network. 相似文献
7.
The reaction of {HB(Me 2pz) 3}Mo(NCS)(S 4) [HB(Me 2pz) 3− = hydrotris(3,5-dimethylpyrazolyl)borate anion] with dicarbomethoxyacetylene in refluxing toluene results in the formation of the brown, diamagnetic complex {HB(Me 2pz) 3}Mo(NCS){S 2C 2(CO 2Me) 2} (1) (the reactants above also yield 1 upon prolonged reaction in dichloromethane at 25°C), which has been characterized by X-ray crystallography. The mononuclear pseudo-octahedral complex contains a facially tridentate HB(Me 2pz) 3− ligand, a monodentate N-bound NCS − ligand, and a bidentate S 2C 2(CO 2Me) 22− ligand having a near planar MoS 2C 4 fragment and a SC=CS bond distance of 1.342(15) Å. Solutions of 1 are unstable in air and decompose to produce {HB(Me 2pz) 3}MoO 2(NCS) and {HB(Me 2pz) 3}MoO(NCS) 2. 相似文献
8.
The copper compound [(THF)KCu(O tBu) 3] ∞ 1 was obtained by interaction of a 1:1 mixture of ZnCl 2/CuCl 2 with KO tBu. Bi- and trifunctional aminoalcohols were used to synthesize the intramolecularly donor stabilized Cu(II) alkoxides Cu(OCH(R)CH 2NMe 2) 2 (3: R=Me, 4: =CH 2NMe 2) where 4 was structurally characterized. Lewis acid–base adduct formation with (Me 3Si) 3CZnCl gave the heterodinuclear compounds (Me 3Si) 3CZnCl · Cu(OCH(R)CH 2NMe 2) 2 (5: R=Me, 6: R=CH 2NMe 2), which were characterized by X-ray single-crystal structure analysis. The two metal centers Cu and Zn of 5 and 6 are bridged by two oxygen atoms to form a Cu–O–Zn core. Pyrolysis of compounds 5 and 6 in dry argon or a H 2/N 2 mixture at atmospheric pressure forms metallic copper and zinc oxide, whereas pyrolysis under O 2/Ar forms additionally oxidized copper species. Elemental analysis of the pyrolysis products showed carbon and nitrogen contamination. Scanning electron microscopy and energy dispersive X-ray analysis were performed to get information on the morphology and the chemical composition of the pyrolysis products. 相似文献
9.
Heating of the lithium magnesate [Li(THF) 2(μ-Br) 2Mg(Tsi)(THF)] (Tsi = (Me 3Si) 3C) under vacuum gives the dialkylmagnesium compound Mg(Tsi) 2, the first two-coordinate magnesium derivative to have been structurally characterized in the solid state. The compound is remarkably thermally stable, not decomposing (or melting) when heated to 350°C. It has a very low reactivity, failing to react in toluene with, for example, CO 2, Me 3SiCl, Me 2SiHCl, MeI, BCl 3 or CH 3COCl, and even with neat CH 3COCl at its boiling point. It does react, though fairly slowly, with I 2 in toluene to give TsiI, and more rapidly with Br 2 to give TsiBr, and with an excess of PhSO 2Cl in toluene at 1OO°C to give TsiCl. It decomposes quickly in the air, and reacts readily with MeOH in toluene to give TsiH without formation of detectable amounts of the intermediate TsiMgOMe, and with O 2 in toluene. 相似文献
10.
Addition of the diarylstannylene R″ 2Sn (R″ = 2− tBu−4,5,6-Me 3C 6H) to the cryptodiborylcarbene (Me 3Si) 2C(B tBu) 2C furnishes the stannaethene (Me 3Si) 2C(B tBu) 2C=SnR″ 2 (10). The X-ray structure analysis of 10 reveals a strictly planar environment of the tricoordinated tin and carbon atoms and a slight twisting of the Sn=C double bond. 相似文献
11.
The reactions of RNHSi(Me) 2Cl (1, R= t-Bu; 2, R=2,6-(Me 2CH) 2C 6H 3) with the carborane ligands, nido-1-Na(C 4H 8O)-2,3-(SiMe 3) 2-2,3-C 2B 4H 5 (3) and Li[ closo-1-R′-1,2-C 2B 10H 10] (4), produced two kinds of neutral ligand precursors, nido-5-[Si(Me) 2N(H)R]-2,3-(SiMe 3) 2-2,3-C 2B 4H 5, (5, R= t-Bu) and closo-1-R′-2-[Si(Me) 2N(H)R]-1,2-C 2B 10H 10 (6, R= t-Bu, R′=Ph; 7, R=2,6-(Me 2CH) 2C 6H 3, R′=H), in 85, 92, and 95% yields, respectively. Treatment of closo-2-[Si(Me) 2NH(2,6-(Me 2CH) 2C 6H 3)]-1,2-C 2B 10H 11 (7) with three equivalents of freshly cut sodium metal in the presence of naphthalene produced the corresponding cage-opened sodium salt of the “carbons apart” carborane trianion, [ nido-3-{Si(Me) 2N(2,6-(Me 2CH) 2C 6H 3)}-1,3-C 2B 10H 11] 3− (8) in almost quantitative yield. The reaction of the trianion, 8, with anhydrous MCl 4 (M=Ti and Zr) in 1:1 molar ratio in dry tetrahydrofuran (THF) at −78 °C, resulted in the formation of the corresponding half-sandwich neutral d 0-metallacarborane, closo-1-M[(Cl)(THF) n]-2-[1′-η 1σ-N(2,6-(Me 2CH) 2C 6H 3)(Me) 2Si]-2,4-η 6-C 2B 10H 11 (M=Ti (9), n=0; M=Zr (10), n=1) in 47 and 36% yields, respectively. All compounds were characterized by elemental analysis, 1H-, 11B-, and 13C-NMR spectra and IR spectra. The carborane ligand, 7, was also characterized by single crystal X-ray diffraction. Compound 7 crystallizes in the monoclinic space group P2 1/ c with a=8.2357(19) Å, b=28.686(7) Å, c=9.921(2) Å; β=93.482(4)°; V=2339.5(9) Å 3, and Z=4. The final refinements of 7 converged at R=0.0736; wR=0.1494; GOF=1.372 for observed reflections. 相似文献
12.
The reactions of (Me 2AlH) 3 with Me 2AsNMe 2, MeAs(NMe 2) 2, and As(NMe 2) 3 were investigated as a function of time at room temperature and over the temperature range −90 to 24°C by use of 1H and 13C NMR spectroscopy. (Me 2AlH) 3 was found to be very reactive toward the aminoarsines, even at −90°C, and no stable Me 2AlH-aminoarsine adducts were observed. Instead, the initial stages of the reactions involved AS---N bond cleavage with the generation of highly reactive AlN- and AsH-bonded species. The subsequent course of each reaction and the final arsenic-containing product distribution depended upon the original AL:N stoichiometric ratio and the respective aminoarsine. When the Al:N ratio was 1:1, the reactions were straightforward for each aminoarsine. However, in every case, [Me 2AlNMe 2] 2 was the final AlN-containing product. Independent reactions were carried out to verify many of the proposed decomposition pathways that lead to thermodynamically stable products. The results of this study are compared with those of the analogous, previously reported (Me 3Al) 2-aminoarsine systems. Additionally, a new synthetic route to [Me 2AlAsMe 2] 3 has been established from the reaction of (Me 2AlH) 3 with Me 2AsH. 相似文献
13.
Alkylidene complexes (Me 3SiCH 2) 3Ta(PMe 3)=CHSiMe 3 (1) and Me 3SiCH 2Ta(PMe 3) 2(=CHSiMe 3) 2 (3a) were found to react with phenylsilanes H 2SiR′Ph (R′=Me, Ph) and (PhSiH 2) 2CH 2 to give disilyl-substituted alkylidenes (Me 3SiCH 2) 3Ta=C(SiMe 3)(SiHR′Ph) (2) and novel metallasilacyclobutadiene and metalladisilacyclohexadiene complexes. Silyl-substituted alkylidene complex (Bu tCH 2) 2W(=O)[=C(Bu t)(SiPh 2Bu t)] (5a) was prepared from the reaction of O 2 with an equilibrium mixture (Bu tCH 2)W(=CHBu t) 2(SiPh 2Bu t) (4b) (Bu tCH 2) 2W(CBu t)(SiPh 2Bu t) (4a). Our recent studies of the preparation of these complexes and mechanistic pathways in the formation of these silyl-substituted alkylidene complexes are summarized. 相似文献
14.
The title complex (Me 2SiSiMe 2)(η 5-l-indenyl)Fe(CO)] 2(μ-CO) 2 (1) was prepared by the reaction of 1,2-bis(1-indenyl)tetramethyl-disilane and Fe(CO) 5 in refluxing heptane. Its thermal rearrangement product [Me 2Si(η 5-1-indenyl)Fe(CO) 2] 2 (2) was also obtained from the reaction. 1 in refluxing xylene can be readily converted into 2. The crystal structures of the cis isomer 1c and the trans isomer 2t were determined by X-ray diffraction. 相似文献
15.
UV/vis in diffusion reflection mode (DRS) and DRIFT spectroscopy have been used to study the surface zirconocene species formed at the interaction of Me 2Si(Ind) 2ZrCl 2 and Me 2Si(Ind) 2ZrMe 2 complexes with the MAO/SiO 2 support. Effect of additional activation of these catalysts with TIBA has been studied as well. Structure of type [Me2Si(Ind)2ZrMe]+[MeMAO]− (C) is formed at the reaction of Me2Si(Ind)2ZrMe2 complex with MAO/SiO2 (a.b. at 456 nm in UV/vis spectra). Interaction of this complex with TIBA results in the formation of new structure (D) with a.b. at 496 nm in UV/vis spectra. The surface species of different composition and structures are formed at interaction of Me2Si(Ind)2ZrCl2 complex with MAO/SiO2. The ratio between these species depends on the zirconium content in the Me2Si(Ind)2ZrCl2/MAO/SiO2 catalysts. According to the DRIFTS data (CO and ethylene adsorption) and ethylene polymerization data these catalysts contain active ZrMe bonds but activity of these catalysts at ethylene polymerization is low. Interaction of Me2Si(Ind)2ZrCl2/MAO/SiO2 with TIBA leads to the formation of the new cationic structure of type (D) with a.b. at 496 nm in UV/vis spectra and great increasing of activity at ethylene polymerization. 相似文献
16.
During thermolysis of the 7-germanorbornadiene 1 in chlorobenzene at 70°C in the presence of concentrated hydrochloric acid, besides the well-known formation of free germylene Me 2Ge and its consecutive product dimethylchlorogermane 2, the polar splitting of only one Ge---C bond in 1 has been observed for the first time. It does not yield Me 2Ge, but instead it rapidly forms the 1-germyl-1,4-dihydronaphthalene 3. The kinetics of this reaction at 53°C are of 2nd order, t1/2 = 20 min, k = 0.22 l mol −1 min −1. At room temperature 3 is formed quantitatively. Also, at 70°C the slower formation of the germylene Me 2Ge from 1 can be suppressed completely if HCl gas is bubbled through the reaction mixture, thus favouring the rapid formation of 3. As a by-product the 1,2-dihydronaphthalene 5 is generated. 相似文献
17.
Transamination reactions utilizing the compound mercuric bis(trimethylsilyl)amide, Hg{N(SiMe 3) 2} 2, in tetrahydrofuran (THF), and the metals Na, Mg, Ca, Sr, Ba and Al have been investigated. Thus the THF solvated compounds Na[N(SiMe 3) 2]·THF and M[N(SiMe 3) 2] 2·2THF, M = Mg, Ca, Sr and Ba (1–4), have been prepared. The X-ray crystal structures of 1 and the related manganese compound Mn[N(SiMe 3) 2] 2·2THF (5) are reported. Interaction of the silylamides, 2–4, with a range of crown ethers apparently proceeded with elimination of silylamine, (Me 3Si) 2NH, and novel ring opening of the crown ethers, generating species containing a donor alkoxide ligand with a vinyl ether function, presumably, ---O(CH 2CH 2O) nCH=CH 2 ( n = 3−5). The silylamides 2–4 were also cleanly converted to the corresponding alkoxides (from 1H NMR data) in reactions with stoichiometric quantities of 3-ethyl-3-pentanol. 相似文献
18.
The new chloro(cyclopentadienyl)silanes Cp′SiH yCl 3−y (Cp′=Me 4EtC 5, y=1: 1; Cp′=Me 4C 5H, y=1: 2; y=0: 3; Cp′=Me 3C 5H 2, y=1: 4 and pentachloro(cyclopentadienyl)disilanes Cp′Si 2Cl 5 (Cp′=Me 5C 5 5, Me 4EtC 5 6, Me 4C 5H 7, Me 3C 5H 2 8, Me 3SiC 5H 4 9) are synthesized in good yields via metathesis reactions. Treatment of 1–9 with LiAlH 4 leads under Cl–H exchange to the hydridosilyl compounds Cp′SiH 3 (Cp′=Me 4EtC 5 10, Me 4C 5H 11, Me 3C 5H 2 12) and to the hydridodisilanyl compounds Cp′Si 2H 5 (Cp′=Me 5C 5 13, Me 4EtC 5 14, Me 4C 5H 15, Me 3C 5H 2 16, Me 3SiC 5H 4 17). Complexes 1–17 are characterized by 1H, 13C, and 29Si-NMR spectroscopy, IR spectroscopy, mass spectrometry and CH-analysis. The structures of 6, 7 and 9 are determined by single-crystal X-ray diffraction analysis. Pyrolysis studies of the cyclopentadienylsilanes 10–12 and disilanes 13–17 show their suitability as precursors in the MOCVD process. 相似文献
19.
对近年来含硅有机锡化合物的进展进行了综述,结构和活性关系的研究表明化合物的生物活性主要取决于硅原子上的取代基,生物活性大小顺序为:(Me 3SiCH 2) 3SnY>>(PhMe 2SiCH 2) 3SnY>(Ph 2MeSiCH 2) 3SnY,(PhCH 2Me 2SiCH 2) 3SnY. 相似文献
20.
The compounds M[(N-t-Bu) 2SiMe 2] 2 (I M = Ti; II, M = Zr) were prepared by treatment of dilithiated Me 2Si(NH-t-Bu) 2 with TiCl 4 and ZrCl 4, respectively. Crystals of I and II belong to the space groups P2 12 12 1 and C2/ c, respectively. The spirocyclic molecules possess approximate D2d symmetry with planar MN 2Si rings. Important ring dimensions are d(MN) 1.890(4)/2.053(2) » (I/II). d(SiN) 1.742(10)/1.753(2) », angle NMN 83.4(2)/77.9(1)° and angle NSiN 92.4(2)/94.8(1)°. 相似文献
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