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1.
The syntheses of Bromodisilanes Br nSi 2H 6−n and Iododisilanes I nSi 2H 6−n ( n = 1, 2, 3, 4, 5), starting from caryldisilanes Ar nSi 2H 6−n (Ar = phenyl, -naphthyl, mesityl) are reported. The 29Si-NMR-spectra of all compounds, including 29Si 29Si-coupling constants, have been measured. ZusammenfassungAusgehend von Aryldisilanen ArS2H6−n, (Ar = Phenyl, -Naphthyl, Mesityl) wurden die Bromdisilane BrnSi2H6−n, und Ioddisilane InSi2H6−n, (n = 1, 2, 3, 4, 5) synthetisiert. Die 29Si-NMR-Spektren aller Verbindungen, (eingeschlossen 29Si29Si-Kopplungskonstanten) wurden vermessen. 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.
139La-NMR chemical shifts were measured for several anionic complexes of formulae Li(C 4H 8O 2) 3/2 [La(ν 3-C 3H 5) 4], [Li(C 4H 8O 2) 2][Cp′ nLa(ν 3-C 3]H 5) 4−n] (Cp′ = Cp(ν 5-C 5H 5); n = 1, 2 and Cp′ = Cp * (ν 5-C 5Me5); N = 1) and Li[R nLa(ν 3-C 3H 4) 4− n] (R = N(SiMe 3) 2; n = 1, 2 and R = CCsIMe 3; n = 4), as well as for neutral compounds for formulae La(ν 3-C 3H 5) 3L n (L = (C 4H 8O 2) 1.5, (HMPT) 2, TMED), Cp′ nLa(ν 3-C 3H 5) 3−n (Cp′= Cp(ν 5-Cp 5H 5), Cp *(ν 5-C 5Me 5); n = 1, 2) and La(ν 3-C 3H 2) 2X(THF) 2 X = Cl, Br, I). Typical ranges of the 139La-NMR chemical shifts were found for the different types of complex independent of number and kind of organyl groups directly bonded to lanthanum. Zusammenfassung139La-NMR-Spektroskopie wurde an einer Reihe anionischer Allyllanthanat(III)-Komplexe der Zusammensetzung
]- [La)ν3-C3H5)4, [Li(C4H8)2][Cp′nLa(ν3-C3H5)4−n(Cp′ = Cp(ν5-C5H5); n = 1, 2 und Cp′ = Cp * (ν5-C5Me5); N = 1) und Li[RnLa(ν3-C3H5)4−n (R = B(SiMe3)2; n = 1, 2 und R = CCSiMe3; n = 4 sowie neutraler Allyllanthan(III)-Komplexe der Zusammensetzung La(ν3-C3H5)3Ln (Ln = (C4H8O2)1.5, (HMPT)2, TMED), Cp′n, La(ν3-C3H5)3−n (Cp′ = Cp(ν5-C5H5), Cp * (ν5- Cp5Me5); n = 1, 2) und La(ν3-Cp3H5)2X(THF)2 (X = Cl, Br, I) durchgefürt. In Abhängikeit von der Anzahl und der Art der am Lanthan gebundenen Gruppen wurden für die verschieden Komplextypen charakteristische Resonanzbereiche ermittelt. 相似文献
4.
合成了标题化合物并测定其晶体结构.晶体属三斜晶系,P1空间群,α=0.80284(8)nm,b=0.95993(6)nm,c=0.71660(9)nm,α=102.016(9)°,β=111.933(9)°,γ=101.650(8)°,V=0.4767(1)nm 3,Z=1,D c=3.21g·cm -3,F(000)=404,μ(MoK a)=98.77cm -1.晶体中存在反式平面型的(2,2'-bipyH 2) 2+阳离子和线性的I 3-阴离子.晶体由[(2,2'-bipyH 2)(I 3) 2] ∞链堆积而成,同一层的链间存在N-H···I氢键,氢键键长N···I为0.349nm.用UV-Vis光谱和 1H NMR谱对标题化合物进行了表征. 相似文献
5.
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
6.
The coordinatively unsaturated uranium(IV) complex U[N(C 6H 5) 2] 4 has been prepared via the stoichiometric reaction of diphenylamine with [(Me 3Si) 2N] 2
H 2. U[N(C 6H 5) 2] 4 coordinates Lewis bases such as Et 2O, THF, pyridine or (EtO) 3PO, based on electronic absorption spectroscopy and 1H NMR studies. Exchange between U[N(C 6H 5) 2] 4 and U[N(C 6H 5) 2] 4(L), where L is THF or pyridine, is rapid on the NMR time-scale between 307 and 323 K. Measurement of equilibrium constants for L = THF provides Δ H and Δ S values of −60 kJ mol −1 and −1.8 × 10 2 J K −1 mol −1, respectively. U[N(C 6H 5) 2] 4 coordinates and binds (EtO) 3PO much more tightly ( Keq = & > 10 4 M −1) than THF or pyridine with the exchange rate between U[N(C 6H 5) 2] 4 and U[N(C 6H 5) 2] 4[OP(OEt) 3] being close to the NMR time-scale. 相似文献
7.
The new iodoammonium salts o-C 6H 4(NH 2) 2I +I − (1) and o-C 6H 4(NH 2) 2I + AsF 6− (2) were prepared by reaction of o-phenylene diamine with I 2 or I 3+AsF 6−, respectively. Compound 1 reacts with AlI 3 yielding quantitatively the corresponding tetraiodoaluminate o-C 6H 4(NH 2) 2I +AlI 4− (3). The species were characterized by chemical analysis, vibrational (IR and Raman) and temperature-dependent 1H NMR spectropscopy. Direct evidence for a N---I bond was found in the Raman spectra of 1, 2 and 3 (ν(NI) = 599–600 cm −1). 相似文献
8.
The synthesis of the potential bridging ligand (C 6H 5) 2PCH 2CH 2Si(CH 3) 2C 5H 4 (3) is described. The ferrocene (6 derived from 3 has been found to form macrocyclic complexes with metal fragments NiCl 2, NiBr 2, and Co 2(CO) 6. Although monomeric, bimetallic products might have been expected based upon the reduced steric demands of ligand 3 relative to an analogous ligand, (C 6H 5) 2PCH 2Si(CH) 3) 2C 5H 4 (1), it appears that the increased flexibility in 3 is the overriding factor leading to a preference for inter- rather than intramolecular coordination of the second phosphine function in 6. 相似文献
9.
The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO +, RNC, RN 2+ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH 3OC 6H 4N 2Mo(CO) 2C 5H 5 was prepared by the reaction of NaMo(CO) 3C 5H 5 with p-CH 3OC 6H 4N 2+BF 4−. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN 2M(CO) 2C 5H 5, RN 2M(CO) 2(Pz 3BH) (M = Cr, Mo, W), [(η 6-Me 6C 6)Cr(CO) 2N 2Ar] +, [(MeC 15H 4)M′(CO) 2N 2Ar] + M′ = Mn, Re), [ trans-PhN 2Fe(CO) 2(PPh 3) 2] +, and PhN 2M′(CO) 2(PPh 3) 2(PPh 3) 2 can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH 2N 2M(CO) 2C 5H 5 (R = H or Me 3Si) can be obtained from HM(CO) 3C 5H 5 and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN 2M(CO) 2Q derivatives (Q = C 5H 5, Pz 3BH) include CO substitution reactions, coordination of the second nitrogen in the RN 2 ligand to give heterobimetallic complexes such as C 5H 5Mo(CO) 2(μ-NNC 6H 4Me)(CO) 2C 5H 5, oxidative addition rections with X 2 X = Cl, Br, I), SnX 4, RSSR, and CINO, and reactions with further RN 2+ to give bis(aryldiazenido) derivatives (RN 2) 2MQL + (L = CO, X −, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC 5H 4)M′(CO) 2N 2Ar] + with certain nucleophiles to give (MeC 5H 4)M′(CO) 2N 2. 相似文献
10.
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
11.
H CIDNP spectra recorded during the decomposition of aliphatic diacyl peroxides ((RCOO)2 R=n-C H (1),n-c5H11(2)) in ODCB in the presence of scavengers,such as I2C2H5I,(CH3)2CHI,and CH2=CHCH2 Br show multiplet effect for the scavenged products,RX(X=Br,I) and for disproportionation products,R-H.The reactionmechanism is discussed in terms of radical pair theory. 相似文献
12.
三(三甲基硅)环戊二烯与六羰基钼在二甲苯中回流8h,反应停留在生成中间物η 5-[(Me 3Si) NC 5H 5-n]Mo(CO) 3H(n=2,3)(I)的阶段.不经分离,I随即分别与CCl 4·NBS及MeI反应,生成其相应的钼卤化物η- 5[(Me 3Si) NC 5H 5-n]Mo(CO) 3X[n=3,X=Cl(1),Br(2),I(3);n=2,X=Cl(4),Br(5),I(6)].4-6是由于茂环上脱掉1个Me 3Si基.经元素分析和IR及 1H NMR谱表征了化合物1-6的结构,并用X射线衍射测定了1的晶体结构. 相似文献
13.
采用多种芳香双酯作为电子给予体制备了丙烯聚合高效催化剂,该催化剂具有高活性、聚合反应平稳、产物等规度高等特征.研究了多种芳香双酯和外加各种烷基硅氧烷对丙烯聚合的作用,测定了聚合反应动力学曲线,确定了聚合动力学方程.用扫描电镜研究了催化剂的形态,表明双酯组份能使催化剂结合得较紧密;对聚合产物的结构用DSD、红外光谱进行了表征. 相似文献
14.
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
15.
Reactions of [(η 6-arene)RuCl 2] 2 (1) (η 6-arene= p-cymene (1a), 1,3,5-Me 3C 6H 3 (1b), 1,2,3-Me 3C 6H 3 (1c) 1,2,3,4-Me 4C 6H 2(1d), 1,2,3,5-Me 4C 6H 2 (1e) and C 6Me 6 (1f)) or [Cp*MCl 2] 2 (M=Rh (2), Ir (3); Cp*=C 5Me 5) with 4-isocyanoazobenzene (RNC) and 4,4′-diisocyanoazobenzene (CN–R–NC) gave mononuclear and dinuclear complexes, [(η 6-arene)Ru(CNC 6H 4N=NC 6H 5)Cl 2] (4a–f), [Cp*M(CNC 6H 4N=NC 6H 5)Cl 2] (5: M=Rh; 6: M=Ir) , [{(η 6-arene)RuCl 2} 2{μ-CNC 6H 4N=NC 6H 4NC}] (8a–f) and [(Cp*MCl 2) 2(μ-CNC 6H 4N=NC 6H 4NC)}] (9: M=Rh; 10: M=Ir) , respectively. It was confirmed by X-ray analyses of 4a and 5 that these complexes have trans-forms for the ---N=N--- moieties. Reaction of [Cp*Rh(dppf)(MeCN)](PF 6) 2 (dppf=1,1′-bis (diphenylphosphino)ferrocene) with 4-isocyanoazobenzene gave [Cp*Rh(dppf)(CNC 6H 4N=NC 6H 5)](PF 6) 2 (7), confirmed by X-ray analysis. Complex 8b reacted with Ag(CF 3SO 3), giving a rectangular tetranuclear complex 11b, [{(η 6-1,3,5-Me 3C 6H 3)Ru(μ-Cl} 4(μ-CNC 6H 4N=NC 6H 4NC) 2](CF 3SO 3) 4 bridged by four Cl atoms and two μ-diisocyanoazobenzene ligands. Photochemical reactions of the ruthenium complexes (4 and 8) led to the decomposition of the complexes, whereas those of 5, 7, 9 and 10 underwent a trans-to- cis isomerization. In the electrochemical reactions the reductive waves about −1.50 V for 4 and −1.44 V for 8 are due to the reduction of azo group, [---N=N---]→[---N=N---] 2−. The irreversible oxidative waves at ca. 0.87 V for the 4 and at ca. 0.85 V for 8 came from the oxidation of Ru(II)→Ru(III). 相似文献
16.
利用(μ 3-CCO 2Et)Co 3(CO) 9与单阴离子试剂[Mo(CO) 3(η 5-C 5H 4R)]-[R=H,C(O)Me]的反应合成了2个新的含CCo 2Mo骨架的簇合物(μ 3-CCO 2Et)Co 2Mo(CO) 8(η 5-C 5H 4R)[R=H(1);R=C(O)Me(2)],进而用其与双阴离子试剂{-M(CO) 3[η 5-C 5H 4C(O)]} 2-1,4-C 6H 4[M=Mo,W]反应合成了4个双四面体簇合物{(μ 3-CCO 2Et)CoMoM(CO) 7(η 5-C 5H 4R)[η 5-C 5H 4C(O)]} 2-1,4-C 6H 4[M=Mo,R=H(3);M=Mo,R=C(O)Me(4);M=W,R=H(5);M=W,R=C(O)Me(6)].这6个化合物的C和H元素分析,IR, 1HNMR等表征都与其结构一致.晶体X射线衍射分析表明,化合物2属单斜晶系,C 2/c空间群,晶胞参数a=1.1264(3)nm,b=1.1879(3)nm,c=3.3565(10)nm,β=93.320(5)°,V=4.484(2)nm 3,Z=8,D c=1.867g·cm -3,F(000)=2480,R=0.0369,wR=0.1150. 相似文献
17.
The siloxyanilines o-Me 3SiOC 6H 4NH 2 (1) and p-RMe 2SiOC 6H 4NH 2 (R=H (2); R=Me (3)), and their N-silylated derivatives p-Me 3SiOC 6H 4NHSiMe 3 (4) and p-Me 3SiOC 6H 4N(SiMe 3) 2 (5) have been prepared from ortho- or para-aminophenol and used in the synthesis of imido complexes. Thus, binuclear [{Ti(η 5-C 5H 5)Cl}{μ-NC 6H 4( p-OSiMe 3)}] 2 (6) and mononuclear [TiCl 2{NC 6H 4( p-OSiMe 3)}(py) 3] (7) imido complexes have been obtained from the reaction of 3 and [Ti(η 5-C 5H 5)Cl 3] or [TiCl 2(N tBu)(py) 3], respectively. In contrast, the reaction of 1 with TiCl 4 and tBupy affords the titanocycle [TiCl 2{OC 6H 4( o-NH)---N,O}( tBupy) 2] (8). Compound 5 has also been used to prepare the niobium imide complex [NbCl 3{NC 6H 4( p-OSiMe 3)}(MeCN) 2] (9), by its reaction with NbCl 5 in CH 3CN. These findings have been applied to the synthesis of polynuclear systems. Thus, chlorocarbosilane Si[CH 2CH 2CH 2Si(Me) 2Cl] 4 (CS–Cl) has been functionalized with the ortho- and para-aminophenoxy groups to give 10 and 11, respectively. The use of 11 has allowed the formation of the tetranuclear compound 12. Attempts to synthesize terminal imido titanium complexes from 10 and TiCl 4 in the presence of tBupy and Et 3N, give complex 8 and carbosilane CS–Cl. 相似文献
18.
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
19.
Bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (2-(CH 3) 2N-C 9H 6) 2ZrCl 2, and dimethylsilyl-bridged bis(2-N,N-dimethylamino-indenyl) zirconium dichloride, (CH 3) 2Si(2-(CH 3) 2N-C 9H 5) 2ZrCl 2, were prepared by reaction of the corresponding ligand lithium salts with ZrCl 4 in toluene. Diffractometric structure determinations reveal C 2-symmetric complex geometries for both complexes. An increased electron density at the Zr center of the dimethylamino-substituted complexes is indicated by reduction potentials which are 0.3–0.4 V more negative than those of their unsubstituted analogs. When activated with methyl aluminoxane in toluene solution, (CH 3) 2Si(2-(CH 3) 2N-C 9H 5) 2ZrCl 2 catalyzes the polymerization of propene to polymers with a microstructure comparable with that of polymers produced with other Me 2Si-bridged bis(indenyl)ZrCl 2 complexes, but with a substantially increased fraction of i-propyl end groups derived from alkyl exchange between Zr-polymer and Al---Me species. 相似文献
20.
The complex C 5H 5(PMe 3)Co(μ-CS) 2CoC 5H 5 (I) is formed by the reaction of C 5H 5Co(PMe 3)CS and CH 2I 2. The X-ray structure analysis shows an unsymmetrical non-planar Co 2C 2-skeleton with different Co---C bond lengths. The Co---Co distance is 239.2 pm. Compound I thus represents a new example of binuclear (18 + 16)-electron complexes in which the more electron-rich metal atom forms a donor bond to the more electron-poor counterpart. The reaction of I with ligands such as P(NMe 2) 3 does not lead to bridge cleavage indicating the stability of the Co(CS) 2Co-framework. 相似文献
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