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1.
The diol R 2C(SiMe 2OH) 2 (R = Me 3Si) has been shown to react with: SO 2Cl 2 to give R 2
Me 2; SOCl 2 to give R 2C(SiMe 2Cl) 2; Me 3SiI or Me 3SiCl to give R 2C(SiMe 2OSiMe 3) 2; R′COCl; (R′ = Me or CF 3) to give R 2C(SiMe 2O 2CR′)-(SiMe 2Cl); (R′CO) 2O (R′ = Me or CF 3 to give R 2C(SiMe 2O 2CR′) 2; with MeOH containing acid to give R 2C(SiMe 2OMe) 2; with neutral MeOH to give R 2C-(SiMe 2OMe) 2 and probably R 2
Me 2; MeLi to give R 2C(SiMe 2OLi) 2 (and the latter to react with PhMeSiF 2 to give R 2
Me 2). The diacetate R 2C(SiMe 2O 2CMe) 2 reacts with CsF in MeCN to give R 2C(SiMe 2F) 2; it does not react with NaN 3 or KSCN in MeCN, but the bis(trifluoroacetate) reacts with these salts with KOCN to give R 2C(SiMe 2X) 2 (X = N 3, NCS, NCO). 相似文献
2.
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
3.
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
4.
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
5.
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
6.
Protonation of the lithium triphospha-cyclopentenyl salt Li (P 3C 2Bu t2RR′) (R=(Me 3Si) 2CH-, R′=Bu n) with HCl affords the new 2,3-dihydro-1 H-[1,2,4] triphosphole P 3C 2Bu t2(H) (Bu n)CH(SiMe 3) 2 which has been structurally characterised as its [W(CO) 5] complex. 相似文献
7.
碳锗双桥连二环戊二烯(Me 2C)(Me 2Ge)(C 5H 4) 2(1)与五羰基铁在回流甲苯及二甲苯中的反应,得到正常的Fe-Fe键化合物(Me 2C)(Me 2Ge)[(η 5-C 5H 3)Fe(CO)] 2(μ-CO) 2(3)和脱锗桥产物(Me 2C)[(η 5-C 5H 4)Fe(CO)] 2(μ-CO) 2(4)以及一个结构新颖的化合物(Me 2C)[(η 5-C 5H 3)[(Me 2Ge)Fe(CO) 2](η 1,η 5-C 5H 3)[Fe(CO) 2](2).用X射线衍射分析測定了化合物3的晶体结构,并提出了可能的生成机理. 相似文献
8.
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
9.
The compound ( o-MeC 6H 4Me 2Si) 3CH has been prepared and shown to be metallated slowly by MeLi in refluxing THF to give the lithium reagent ( o-MeC 6H 4Me 2Si) 3CLi. This reacts with MeI to give ( o-MeC 6H 4Me 2Si) 3CMe, but not with Me 2SiHCl nor with a range of other organosilicon halides. 相似文献
10.
Sodium bis(trimethylstannyl)amide NaN(SnMe 3) 2, isolated by the reaction of trimethylstannyldiethylamine with sodium amide, reacts with tris(trimethylsilyl)hydrazino—dichloro-phosphine to form bis(trimethylsilyl)bis(trimethylstannyl)-2-phospha-2-tetrazene, (Me 3Si) 2N-N=P-N(SnMe 3) 2. Both the molecules have been isolated and characterized. 相似文献
11.
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
12.
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
13.
Characteristics of methyl methacrylate (MMA) polymerization using oscillating zirconocene catalysts, (2-Ph-Ind) 2ZrX 2 (X = Cl, 1; X = Me, 2), mixtures of rac- and meso-zirconocene diastereomers, (SBI)ZrMe 2 [3, SBI = Me 2Si(Ind) 2] and (EBI)ZrMe 2 [4, EBI = C 2H 4(Ind) 2], as well as diastereospecific metallocene pairs, rac-4/Cp 2ZrMe 2 (5) and rac-4/CGCTiMe 2 [6, CGC = Me 2Si(Me 4C 5)( t-BuN)], are reported. MMA polymerization using the chloride catalyst precursor 1 activated with a large excess of the modified methyl aluminoxane is sluggish, uncontrolled, and produces atactic PMMA. On the other hand, the polymerization by a 2/1 ratio of 2/B(C 6F 5) 3 or 2/Ph 3CB(C 6F 5) 4 is controlled and produces syndiotactic PMMA. Mixtures of diastereomeric ansa-zirconocenes 3 or 4 containing various rac/ meso ratios, when activated with B(C 6F 5) 3, yield bimodal PMMA; this behavior is attributed to the meso-diastereomer that, in its pure form, affords bimodal, syndio-rich atactic PMMA. For MMA polymerization using diastereospecific metallocene pairs, rac-4/5 and rac-4/6, the isospecific catalyst site dominates the polymerization events under the conditions employed in this study, and the aspecific and syndiospecific sites are largely nonproductive, thereby forming only highly isotactic PMMA. 相似文献
14.
Treatment of the dimer complex [C 5Me 5 (CO) 2 Ru] 2 (1) with HBF 4 in CH 2Cl 2 at room temperature yields the hydrido-bridged dinuclear complex [(C 5Me 5) 2Ru 2(CO) 4H]BF 4 (2), and after refluxing in propionic anhydride [C 5Me 5(CO) 3Ru]BF 4 (5) is obtained, UV-irradiation of 1 in the presence of H 2CHal 2 (Hal = Cl, I) or trimethylphosphine leads to the formation of C 5Me 5(CO) 2Ru-Hal (3a, 3b) or C 5Me 5(CO)(Me 3P)RuH (4) respectively. Exchange reactions of 3a, 3b with LiAlH 4, NaOMe and Me 3 P give the complexes C 5Me 5(CO) 2RuX (6a,6b) (X=H, OMe), C 5Me 5(CO)(Me 3P)Ru-Hal (7a,7b) (Hal = Cl, I) and C 5Me 5(Me 3P) 2RuI (8). The interaction of 3b or 5 with Me 3P=CH 2 leads to the formation of the ylide complex [C 5Me 5(CO)(Me 3P)-RuCH 2PMe 3)Cl (9) or the rutheniumacyl-ylide C 5Me 5(CO) 2RuC(O)CH=PMe 3 (10). 4 reacts with Me 3P=CH 2 to give C 5Me 5(CO)(Me 3P)RuMe (11) and Me 3P via the intermediate formation of the phosphonium salt Me 4P[Ru(CO) (Me 3P)-C 5Me 5]. 相似文献
15.
Photochemical reaction of (CO) 2(dppe)Fe(H)(SiR 3) with HSiR 3 (SiR 3 = Si(OMe) 3, Si(OEt) 3, SiMe 3, SiMe 2Ph, SiPh 3) yields the trihydrido silyl complexes (CO)(dppe)FeH 3(SiR 3 ). The analogous complexes (PR′Ph 2) 3 FeH 3(ER 3) are prepared by reaction of the H 2 -complexes (PR′Ph 2) 3FeH 2(H 2) with HER 3 (ER 3 = SiMe 3, SiMC 2Ph, SiMePh 2, SiPh 3, Si(Me 2)OSi(Me 2)H, SnPh 3, SnEt 3). Additional derivates of (CO) (dppe)FeH 3(SiR 3) (SiR 3 = SiMePh 2) and (PR′Ph 2) 3FeH 3(SiR 3) (SiR 3 = Si(OMe) 3, SiH 2Ph, SiHPh 2, Si(OEt) 3, SiMePhCl) are accessible by silane exchange starting from (CO)(dppe)FeH 3(SiMe 3) and (PR′Ph 2) 3FeH 3(SiMe 3). (PBuPh 2) 3FeH 3(SiMePh 2) was also prepared from (PBuPh 2) 3FeH 2(N 2) and HSiMePh 2, and (PBuPh 2) 3FeH 3(SnMe 3) from (PBuPh 2) 3FeH 2(H 2) and Me 3SnCl. The complex (PBuPh 2) 3FeH 3(SnMe 3) crystallizes as a toluene solvate in the cubic space group I
3d and shows crystallographically imposed C 3-symmetry. The complexes (CO) 2 (dppe)Fe(H)(SiR 3) and (PR′Ph 2) 3FeH 3(ER 3) are highly dynamic in solution. Low temperature NMR measurements and the E, Fe, H coupling constants strongly indicate that the exchange mechanism involves η 2-HER 3 ligands. 相似文献
16.
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
17.
The compounds Cp 2VR (R = CH 3, C 2H 5, n-C 3H 7, n-C 4H 9, n-C 5H 11, CH 2C(CH 3) 3 or CH 2Si(CH 3) 3) have been prepared from Cp 2 VCl and RMgX in n-pentane. The air-sensitive compounds are stable at room temperature, but decompose between 65 and 138°C. The thermal stability decreases in the order R = CH 3 CH 2Si(CH 3) 3 > C 2H 5 > CH 2C(CH 3) 3 > n-C 5H 11 > n-C 4H 9 > n-C 3H 7. Compounds with R = i-C 3H 7 or t-C 4H 9 could not be obtained. 相似文献
18.
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
19.
1,2-二(1-苯基环己基环戊二烯基)四甲基二硅烷与Fe(CO) 5在二甲苯中加热回流生成二铁化合物(Me 2SiSiMe 2)[(1-Ph-c-C 6H 10C 5H 3)Fe(CO)] 2(μ-CO) 2(2).通过柱层析分离到化合物2的顺反异构体2c和2t,并分别进行热重排反应,发现顺式底物2c重排生成反式重排产物[Me 2Si(c-C 6H 10PhC 5H 3)Fe(CO) 2] 2(3t),而反式底物2t重排则生成顺式重排产物3c.这表明重排反应是立体专一性的.通过X射线衍射分析测定了化合物2c和3t的晶体结构. 相似文献
20.
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
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