共查询到20条相似文献,搜索用时 15 毫秒
1.
Marie-Hélène Thibault 《Journal of organometallic chemistry》2011,696(10):2211-2216
NMR study of the reactivity of multifunctional ligand cis,cis-C6H9(NHCH2C6H4-o-PPh2)3 (1) with GaMe3 and Zr(NMe2)4 was carried out, yielding [cis,cis-(κN-NHCH2C6H4-o-PPh2)(κN-NCH2C6H4-o-PPh2)2C6H9]GaMe (2) and [cis,cis-(NCH2C6H4-o-PPh2)3C6H9]Ga2Me3 (3), and [cis,cis-(NCH2C6H4-o-PPh2)3C6H9]Zr(NMe2) (4), respectively. The spectral properties of 2 and 3 are very similar to that observed for the equivalent aluminum species already reported, but form at a much slower rate which allows for the observation of a GaMe3⋅1 adduct. Species 4 undergoes coordination/displacement of one of the phosphine arms, which was observed using both NMR spectroscopy and DFT analyses. 相似文献
2.
[Pd(C6F5)2(CNR)2] (R = Cy, But, p-MeC6H4 (p-Tol)) react with [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2(CNR)2]. In refluxing benzene insertion of isocyanide into the C6F5Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd2 (μ-Cl)2[μ-C(C6F5) = N(Tol-p)]2n]. This complex reacts with (a) Tl(acac) to give [Pd2{μ-C(C6F5) = N(Tol-p)}2(acac)2]; (b) neutral monodentate ligands to afford dimeric complexes [Pd2{μ-C(C6F5) = N(Tol-p)}2Cl2L2] (L = NMe3, py, 4-Me-py, SC4H8), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [(CNR)Cl{μ-C(C6F5) = (p-Tol)}]n (R = p-Tol, Me, But). Thermal decomposition of cis-[Pd2 (μ-Cl)2 [μ-C(C6F5) = N( p-Tol)]2n] gives the diazabutadiene species (p-Tol)NC(C6F5)C(C6F5)N(p-Tol) in high yield. 相似文献
3.
Falguni Basuli 《Journal of organometallic chemistry》2011,696(1):235-243
A series of reactivity studies of the carboamination pre-catalyst [Ti(NMe2)3(NHMe2)][B(C6F5)4] as well as the preparation of other catalysts are reported in this work. Treatment of [Ti(NMe2)3(NHMe2)][B(C6F5)4] with the aldimines Ar′NCHtol (Ar′ = 2,6-Me2C6H3, tol = 4-MeC6H4), and depending on the reaction conditions, results in isolation of [Me2NCHR′][B(C6F5)4] (1) or (Me2N)2CHtol, as well as the asymmetric titanium dimer [(Me2N)2(HNMe2)Ti(μ2-N[2,6-Me2C6H3])2Ti(NHMe2)(NMe2)][B(C6F5)4] (2). Protonation of CpTi(NMe2)3 and Cp∗Ti(NMe2)3 results in isolation of the salts, [CpTi(NMe2)2(NHMe2)][B(C6F5)4] (3) and [Cp∗Ti(NMe2)2(NHMe2)][B(C6F5)4] (4), respectively. Treatment of compounds 3 or 4 with H2N[2,6-iPr2C6H3] results in formation of the imido salts [CpTi(N[2,6-iPr2C6H3])(NHMe2)2][B(C6F5)4] (5) (58% yield) or [Cp∗Ti(N[2,6-iPr2C6H3])(NHMe2)2][B(C6F5)4] (6). When Ti(NMe2)4 is treated with [Et3Si][B(C6F5)4], the salt [Ti(NMe2)3(N[SiEt3]Me2)][B(C6F5)4] (7) is obtained, and treatment of the latter with [2,6-iPr2C6H3]NCHtol produces the imine adduct [Ti(NMe2)3(κ1-[2,6-iPr2C6H3]NCHtol)][B(C6F5)4] (8). The carboamination catalytic activity of complexes 2-7 was investigated and compared to [Ti(NMe2)3(NHMe2)][B(C6F5)4]. Likewise, a proposed mechanism to the active carboamination catalyst stemming from [Ti(NMe2)3(NHMe2)][B(C6F5)4] is described. 相似文献
4.
A new compound dicetyltrimethylammonium hexafluorotitanium dihydrate, [(n-C16H33)N(CH3)3]2[TiF6]·2H2O (compound 1), was hydrothermally synthesized at 150 °C and characterized by single crystal X-ray diffraction, Fourier-transform infrared (FTIR) spectroscopy, elemental analysis, and thermogravimetric analysis. Compound 1 crystallizes in the monoclinic system, space group C2/c. It consists of hexafluorotitanium cations [TiF6]2−, water molecular (H2O), and cetyltrimethylammonium ions [(n-C16H33)N(CH3)3]+, which are connected together by extensive hydrogen bonding. 相似文献
5.
The coupling of aldehydes or ketones with (2-(4-methoxyphenyl)-4-methylenetetrahydrofuran-3-yl)methanol in the presence of nitriles under the influence of 5 mol % tris(pentaflourophenyl)borane at room temperature afforded a novel series of cis-fused hexahydro-1H-furo[3,4-c]pyran derivatives in good yields with high selectivity. This is the first report on the synthesis of hexahydro-1H-furo[3,4-c]pyranyl amide through a sequential Prins/Ritter reactions using B(C6F5)3 as a mild Lewis acid. 相似文献
6.
Lei Wang 《Journal of solid state chemistry》2004,177(1):80-88
Two organically templated zincophosphites, (C6H14N2)·[Zn3(HPO3)4] and (C4H14N2)·[Zn3(HPO3)4] have been prepared under hydrothermal conditions and characterized by single-crystal X-ray diffraction. (C6H14N2)·[Zn3(HPO3)4] crystallizes in the triclinic space group , with cell parameters, a=9.363(4) Å, b=10.051(4) Å, c=10.051(4) Å, α=85.777(13)°, β=82.091(9)°, and γ=79.783(9)°. (C4H14N2)·[Zn3(HPO3)4] crystallizes in the monoclinic space group P21/c, with cell parameters, a=9.9512(3) Å, b=10.1508(3) Å, c=17.8105(5) Å, and β=95.6510(10)°. Although the two structures are different, they have the same anionic framework compositions of [Zn3(HPO3)4]2−. Their frameworks are built up from strictly alternating ZnO4 tetrahedra and HPO3 pseudo pyramids by sharing vertexes. There exist channels with an eight-membered ring window along the a- and c-axis. Powder X-ray diffraction, IR spectroscopy, 31P MAS solid-state NMR, thermogravimetric and differential thermal analyses were also carried out. 相似文献
7.
D. Carmona S. Chaloupka J. Jans R. Thouvenot L.M. Venanzi 《Journal of organometallic chemistry》1984,275(2):303-313
The preparations of cis- and trans-[PtH(C6Cl5)(PEt3)2] by thermal decomposition of cis- and trans-[Pt(OCHO)(C6Cl5)(PEt3)2], respectively, are reported. Also described are cis- and trans-[Pt(SnCl3)(C6Cl5)(PEt3)2], obtained by treating SnCl2 with cis- and trans-[PtCl(C6,Cl5)(PEt3)2], respectively. It is shown that while trans- [PtH(C6Cl5)(PEt3)2] does not form hydride-bridged complexes in the presence of trans-(PtH(MeOH)(PEt3)2]+, the corresponding complex trans-[PtH(C6)(PEt3)2] reacts with the same solvento complex, in methanol, giving labile [(PEt3)2HPt(-μH)Pt(C6F5)(PEt3)2]+. 相似文献
8.
Wen-Yann Yeh Yen-Chung Liu Gene-Hsiang Lee 《Journal of organometallic chemistry》2004,689(6):1014-1018
[Cp4Fe4(CO)4] (1) reacts with p-BrC6H4Li and MeOH in sequence to afford the functionalized cluster [Cp3Fe4(CO)4(C5H4-p-C6H4Br)] (2), while the reaction of 2 with n-BuLi and MeOH produces [Cp2Fe4(CO)4(C5H4Bu)(C5H4-p-C6H4Br)] (3). The double cluster [Cp3Fe4(CO)4(C5H4)]2(p-C6H4) (4) has been prepared by treatment of [Cp4Fe4(CO)4] with p-C6H4Li2 and MeOH in sequence. The electrochemistry of 2 and 4, as well as the crystal structure of 4 have been investigated. 相似文献
9.
Chloride abstraction from [{M(η3 --- C3H5)Cl}n] (M = Pt, n = 4 or M = Pd, n = 2) by (NBu4)2[cis-Pt(C6F5)2(CCSiMe3)2] (1) gives rise to novel homo- and hetero-dinuclear zwitterionic derivatives (NBu4) [{cis-Pt(C6F5)2(CCSiMe3)2}M(η3-C3H5)] (M = Pt 2; M = Pd 3) which are formed by a M(η3-allyl)+ unit attached to both alkynyl ligands of the {cis-Pt(C6F5)2(CCSiMe3)2}2− fragment. The structure of 3 has been established by X-ray diffraction. 相似文献
10.
A. K. Pyartman V. A. Keskinov P. V. Zaitsev N. A. Charykov 《Russian Journal of Inorganic Chemistry》2009,54(8):1323-1328
Phase diagrams on the mole fraction scale are presented for decane- (R4N)2[Nd(NO3)5]-n-octanol(n-butanol, n-decanol) (1–2–3) ternary liquid systems, where R4N+ stands for trialkylbenzylammonium, at T = 298.15 K. The C10H22-(R4N)2[Nd(NO3)5] binary system is a two-phase liquid system. One phase (phase I) is the almost neat solvent; the other (phase II) is enriched in (R4N)2[Nd(NO3)5]. The liquid ternary systems are characterized by homogeneous and two-phase liquid solution fields. One phase is enriched
in (R4N)2[Nd(NO3)5] and n-octanol (n-butanol, n-decanol) and the other in C10H22. The miscibilities in the C10H22-(R4N)2[Nd(NO3)5] binary system and in the ternary liquid systems were used to calculate, from the equations of the nonrandom two-liquid model
(NTRL), intermolecular interaction parameters and excess Gibbs free energies g
E
for the binary and ternary liquid systems along the binodal curve. g
E
> 0 is characteristic of the systems under study, while g
E
decreases in the series of pairs of liquids (1, 2), (1, 3), and (2, 3)
Original Russian Text ? A.K. Pyartman, V.A. Keskinov, P.V. Zaitsev, N.A. Charykov, 2009, published in Zhurnal Neorganicheskoi
Khimii, 2009, Vol. 54, No. 8, pp. 1392–1397. 相似文献
11.
Zhou Li-Ying 《Journal of organometallic chemistry》2007,692(14):2990-2996
The syntheses and structures of a series of new lanthanide complexes supported by a chelating diamide ligand N,N′-bis(trimethylsilyl)-o-phenylenediamine are described. Anhydrous LnCl3 reacts with Li2[o-(Me3SiN)2C6H4], followed by treatment of NaC5H4Me in 1:1:2 molar ratio to afford the corresponding anionic complexes: {[o-(Me3SiN)2C6H4]Ln(MeC5H4)2}{Li(DME)3} [Ln = Yb (1), Sm (2), Nd(3)] in high yield. These complexes were characterized by elemental analysis, IR and 1H NMR. The molecular structures of 1 and 2 were further determined by X-ray diffraction techniques to be an ion-pair complex composed by an anion [o-(Me3SiN)2C6H4]Ln(MeC5H4)2] and a cation [Li(DME)3]. Complexes 1-3 showed high catalytic activity for the polymerization of methyl methacrylate (MMA) at r.t., giving the syndiotactic-rich polymers with relatively narrow molecular weight distributions (Mw/Mn = 1.64-1.82). 相似文献
12.
Holger Hohmeister Peter Müller Isabel Usón Hans-Georg Schmidt Mathias Noltemeyer Jörg Magull 《Journal of fluorine chemistry》2003,120(1):59-64
The fluorination of [MeAlN(2,6-i-Pr2C6H3)]31 using 1 and 2 eq., respectively, trimethyltin fluoride leads to the mono- and difluoro compounds, [FAl(MeAl)2(N(2,6-i-Pr2C6H3))3]·2THF 2 and [(FAl)2MeAl(N(2,6-i-Pr2C6H3))3]·3THF 3, where each methyl group can be selectively exchanged for terminal fluorine atoms (AlF). The reaction of 1 and 3 eq. of trimethyltin fluoride leads to the trifluoro compound [FAlN(2,6-i-Pr2C6H3)]3·3THF 4 and [Me2SnN(2,6-i-Pr2C6H3)]25 as a by-product. The core of compound 5 consists of a tin-nitrogen four-membered Sn2N2 ring. 相似文献
13.
Kang Min Ok 《Journal of solid state chemistry》2007,180(2):446-452
A new uranyl oxyfluoride, [N(C2H5)4]2[(UO2)4(OH2)3F10] has been synthesized by a hydrothermal reaction technique using (C2H5)4NBr, UO2(OCOCH3)2·2H2O, and HF as reagents. The structure of [N(C2H5)4]2[(UO2)4(OH2)3F10] has been determined by a single-crystal X-ray diffraction technique. [N(C2H5)4]2[(UO2)4(OH2)3F10] crystallizes in the monoclinic space group P21/n (No. 14), with , , , β=98.88(3)°, , and Z=4. [N(C2H5)4]2[(UO2)4(OH2)3F10] reveals a novel pseudo-two-dimensional crystal structure that is composed of UO2F5, UO3F4, and UO4F3 pentagonal bipyramids. Each uranyl pentagonal bipyramid shares edges and corners through F atoms to form a six-membered ring. The rings are further interconnected to generate infinite strips running along the b-axis. [N(C2H5)4]2[(UO2)4(OH2)3F10] has been further characterized by elemental analysis, bond valence calculations, Infrared and Raman spectroscopy, and thermogravimetric analysis. 相似文献
14.
Alessandro Fumagalli Thomas F. Koetzle Fusao Takusagawa 《Journal of organometallic chemistry》1981,213(1):365-377
The dianion [RuIr4(CO)15]2- has been obtained by reductive carbonylation of mixtures of Ir4(CO)12 and RuCl3 · χ H2O, and the bis(triphenylphosphine)-iminium salt has been characterized by single-crystal X-ray diffraction techniques. Crystal data: [((C6H5)3P)2N]2[RuIr4(CO)15], space group P (Z 2), a 11.425(3), b 14.141(2), c 25.979(5) Å, α 84.55(1), β 83.53(2), γ 80.71(2)°. The mixed-metal cluster has a structure with an elongated trigonal bipyramidal array of metal atoms in which Ru occupies an apical position. The anion is unstable in vacuum or in an N2 atmosphere yielding predominantly another mixed-metal species which is not as yet fully characterized. Upon reexposure to CO, this latter species is converted back to [RuIr4(CO)15]2-, plus additional products. 相似文献
15.
O. A. Efremova Yu. V. Mironov N. V. Kuratieva K.-K. Wang V. E. Fedorov 《Journal of Structural Chemistry》2010,51(4):782-784
Crystals of the rhenium cluster complex (H3O)4[(C2H5)4N]6[Th2Cl4(H2O)12O]3[Re4Se4(CN)12]4 are obtained in an acidic (HCl) aqueous solution by the reaction of cluster salt K4[Re4Se4(CN)12]·6H2O with ThCl4 and (C2H5)4NCl. Single crystal X-ray analysis shows that the title compound is ionic and crystallizes in the cubic crystal system (a = 22.7322(3) ?, V = 11746.93(27) ?3, Z = 2, I4 3m space group, R = 0.0350). It contains [Th2Cl4(H2O)12O]2+ cations with two thorium atoms bonded to each other through the bridging oxygen atom forming an angle of 180° in the structure. 相似文献
16.
The 1H NMR spectra of C2H5InBr2 · tmen (1) C2H5InI2 · tmen (2) (tmen = N,N,N′,N′-tetramethylethanediamme) and [(C6H5)4P][C2H5InI3] (3) show only a broad singlet for the ethyl protons at 60 MHz. Spectra run at 400 MHz resolve these into a triplet + quartet for 1 and 3. The structure of each compound has been determined by X-ray crystallography; 1 and 2 are five-coordinate species, with InC2N2X (X = Br, I) nuclei, while 3 consists of [(C6H5)4P]+ cations and anions whose InCI3 nucleus has C3v, symmetry. 相似文献
17.
Wendell E. Rhine Jimmy H. Davis Galen Stucky 《Journal of organometallic chemistry》1977,134(2):139-149
The reaction of n-butyllithium chelated to N,N,N′,N′-tetramethylethylenediamine (TMEDA) with acenaphthene results in 1,2-hydrogen abstraction to give the dilithio complex of acenaphthylene, [Li(CH3)2N(CH2)2N(CH3)2]2[C12H8]. This compound was isolated as a crystalline product and characterized by single crystal X-ray crystallography. [Li(CH3)2N(CH2)2N(CH3)2]2[C12H8] crystallizes with a unit cell of a = 23.164(10), b = 25.609(10) and c = 8.495(6) Å in the orthorhombice space group Fdd2. The calculated density is 1.04 g cm?3 for 8 molecules per unit cell. The observed density is 1.03(4) g cm?3. 1412 unique reflections were measured on a full circle X-ray diffractometer. The light atom, acentric structure was solved by the symbolic addition technique and refined by full matrix least squares to R1 = 0.058 and R2 = 0.056.The acenaphthylene fragment is nearly planar. The effect of charge transfer is evidenced in the short C(3)C(4) bond distance of 1.30(3) Å and the lengthening of the C(1)C(2) bond length from the localized olefinic bond distance of 1.34 to 1.42(2) Å. The two LiTMEDA fragments are coordinated to both sides of the five membered carbon atom ring of the acenaphthylene group. 相似文献
18.
Michael Gerken Johnathan P. Mack Reijo J. Suontamo 《Journal of fluorine chemistry》2004,125(11):1663-1670
The salt, [N(CH3)4][IO2F2], was prepared from [N(CH3)4][IO3] and 49% aqueous HF, and characterized by Raman, infrared, and 19F NMR spectroscopy. Crystals of [N(CH3)4]2[IO2F2][HF2] were obtained by reduction of [N(CH3)4][cis-IO2F4] in the presence of [N(CH3)4][F] in CH3CN solvent and were characterized by Raman spectroscopy and single-crystal X-ray diffraction: C2/m, a = 14.6765(2) Å, b = 8.60490(10) Å, c = 13.9572(2) Å, β = 120.2040(10)°, V = 1523.35(3) Å3, Z = 4 and R = 0.0192 at 210 K. The crystal structure consists of two IO2−F2 anions that are symmetrically bridged by two H−F2 anions, forming a [F2O2I(FHF)2IO2F2]4− dimer. The symmetric bridging coordination for the H−F2 anion in this structure represents a new bonding modality for the bifluoride anion. 相似文献
19.
Paz Vaqueiro 《Journal of solid state chemistry》2006,179(1):302-307
Two new main group metal sulphides, [C10N4H26]0.5[InS2] (1) and [C10N4H26]0.5[GaS2] (2) have been prepared solvothermally in the presence of 1,4-bis(3-aminopropyl)piperazine and their crystal structures determined by single-crystal X-ray diffraction. Both compounds are isostructural and crystallise in the monoclinic space group P21/n (Z=4), with a=6.5628(5), b=11.2008(9), c=12.6611(9) Å and β=94.410(4)° (wR=0.035) for compound (1) and a=6.1094(5), b=11.2469(9), c=12.7064(10) Å and β=94.313(4)° (wR=0.021) for compound (2). The structure of [C10N4H26]0.5[MS2] (M=In,Ga) consists of one-dimensional [MS2]− chains which run parallel to the crystallographic a axis and are separated by diprotonated amine molecules. These materials represent the first example of solvothermally prepared one-dimensional gallium and indium sulphides. 相似文献
20.
A promising approach to the unknown type of [Ar′(Ar)IF2]X salts is offered. x-FC6H4IF4 (x=2, 3, 4) reacts with C6F5BF2 in CH2Cl2 and forms [x-FC6H4(C6F5)IF2][BF4] salts in good yields. For [4-FC6H4(C6F5)IF2][BF4] the fluoro-oxidizer property is shown in reactions with weakly reducing agents like E(C6F5)3 (E=P, As, Sb, Bi) and ArI (Ar=4-FC6H4, C6F5). The fluorine/aryl substitution method is also applied to the synthesis of [(4-FC6H4)2IF2][BF4], an example with two identical aryl groups in the difluoroiodonium(V) moiety. 相似文献