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1.
Thermal reaction of the chloroaryl-chloride complexes trans-(η5-C5Me5)Re(CO)2(ArCl)Cl (ArCl = 3-ClC6H4, 3-ClC6H3(4-Me) and 3,5-Cl2C6H3) in acetonitrile did not interconvert to the cis isomer, instead the complex ReCl(CO)2(NCMe)3 and the corresponding 5-ArCl-1,2,3,4,5-pentamethylcyclopentadiene were formed. Similar reductive elimination products were obtained when the starting rhenium complexes were reacted with trimethylphosphite in toluene. 相似文献
2.
Marta Abrantes Isabel S. GonçalvesMartyn Pillinger Carolina VurchioFranca M. Cordero Alberto Brandi 《Tetrahedron letters》2011,52(52):7079-7082
The inorganic-organic hybrid material {[MoO3(bipy)][MoO3(H2O)]}n (bipy = 2,2′-bipyridine) can be used as a water-tolerant catalyst for the oxidation of secondary amines under mild conditions using either urea hydrogen peroxide (UHP) or tert-butylhydroperoxide (TBHP) as the oxidant. Under optimized reaction conditions (2 mol % catalyst, 3-4 equiv TBHP, CH2Cl2 as the solvent, 40 °C), the corresponding nitrones were obtained with different efficiency depending on the nature of the cyclic or acyclic amine used. 相似文献
3.
Mohamed Ali Saada Annie Hémon-Ribaud Vincent Maisonneuve 《Journal of fluorine chemistry》2005,126(7):1072-1077
Tren amine cations [(C2H4NH3)3N]3+ and zirconate or tantalate anions adopt a ternary symmetry in two hydrates, [H3tren]2·(ZrF7)2·9H2O and [H3tren]6·(ZrF7)2·(TaOF6)4·3H2O, which crystallise in R32 space group with aH = 8.871 (2) Å, cH = 38.16 (1) Å and aH = 8.758 (2) Å, cH = 30.112 (9) Å, respectively. Similar [H3tren]2·(MX7)2·H2O (M = Zr, Ta; X = F, O) sheets are found in both structures; they are separated by a water layer (Ow(2)-Ow(3)) in [H3tren]2·(ZrF7)2·9H2O. Dehydration of [H3tren]2·(ZrF7)2·9H2O starts at room temperature and ends at 90 °C to give [H3tren]2·(ZrF7)2·H2O. [H3tren]2·(ZrF7)2·H2O layers remain probably unchanged during this dehydration and the existence of one intermediate [H3tren]2·(ZrF7)2·3H2O hydrate is assumed. Ow(1) molecules are tightly hydrogen bonded with -NH3+ groups and decomposition of [H3tren]2·(ZrF7)2·H2O occurs from 210 °C to 500 °C to give successively [H3tren]2·(ZrF6)·(Zr2F12) (285 °C), an intermediate unknown phase (320 °C) and ZrF4. 相似文献
4.
Treatment of the hydrosulfido tungsten complex CpW(CO)3SH with acid chlorides (RCOCl) or sulfonyl chlorides (RSO2Cl) affords CpW(CO)3SCOR (1) [R = Me (a), CH2Cl (b), Ph (c), 4-C6H4NO2 (d)] and CpW(CO)3SSO2R (2) [R = Me (a), Ph (b), 4-C6H4Cl (c), 4-C6H4NO2 (d)], respectively. The novel complexes, 1 and 2, were fully characterized by elemental analyses, IR and 1H NMR spectroscopy. The solid state structures of CpW(CO)3SCOPh (1c) and CpW(CO)3SSO2-4-C6H4Cl (2c) were determined by an X-ray crystal structure analysis. 相似文献
5.
Claus Feldmann 《Journal of solid state chemistry》2003,172(1):53-58
Preparation and crystal structure of the novel compound [Bi3I(C4H8O3H2)2(C4H8O3H)5]2Bi8I30 are reported. The title compound is prepared by heating of BiI3 and diethylene glycol at 413 K in a sealed quartz glass tube filled with argon. Deep red single crystals are grown and applied to perform X-ray powder diffraction and X-ray single-crystal diffraction measurements. The compound crystallizes triclinic with space group P-1: Z=2, a=13.217(1) Å, b=15.277(1) Å, c=22.498(1) Å, α=84.33(1), β=73.18(1), γ=67.48(1). [Bi3I(C4H8O3H2)2(C4H8O3H)5]2Bi8I30 comprises the novel polynuclear [Bi8I30]6− anion and [Bi3I(C4H8O3H2)2(C4H8O3H)5]3+ as the cation. Cation as well as the anion can be assumed to represent intermediates between solid BiI3 and BiI3 completely dissolved in diethylene glycol. 相似文献
6.
Nomampondomise F. Stuurman 《Journal of organometallic chemistry》2009,694(2):259-9294
The chemical kinetics, studied by UV/Vis, IR and NMR, of the oxidative addition of iodomethane to [Rh((C6H5)COCHCOR)(CO)(PPh3)], with R = (CH2)nCH3, n = 1-3, consists of three consecutive reaction steps that involves isomers of two distinctly different classes of RhIII-alkyl and two distinctly different classes of RhIII-acyl species. Kinetic studies on the first oxidative addition step of [Rh((C6H5)COCHCOR)(CO)(PPh3)] + CH3I to form [Rh((C6H5)COCHCOR)(CH3)(CO)(PPh3)(I)] revealed a second order oxidative addition rate constant approximately 500-600 times faster than that observed for the Monsanto catalyst [Rh(CO)2I2]−. The reaction rate of the first oxidative addition step in chloroform was not influenced by the increasing alkyl chain length of the R group on the β-diketonato ligand: k1 = 0.0333 ([Rh((C6H5)COCHCO(CH2CH3))(CO)(PPh3)]), 0.0437 ([Rh((C6H5)COCHCO(CH2CH2CH3))(CO)(PPh3)]) and 0.0354 dm3 mol−1 s−1 ([Rh((C6H5)COCHCO(CH2CH2CH2CH3))(CO)(PPh3)]). The pKa′ and keto-enol equilibrium constant, Kc, of the β-diketones (C6H5)COCH2COR, along with apparent group electronegativities, χR of the R group of the β-diketones (C6H5)COCH2COR, give a measurement of the electron donating character of the coordinating β-diketonato ligand: (R, pKa′, Kc, χR) = (CH3, 8.70, 12.1, 2.34), (CH2CH3, 9.33, 8.2, 2.31), (CH2CH2CH3, 9.23, 11.5, 2.41) and (CH2CH2CH2CH3, 9.33, 11.6, 2.22). 相似文献
7.
Hydrothermal synthesis in the M/Mo/O (M=Co,Ni) system was investigated. Novel transition metal tetramolybdate dihydrates MMo4O13·2H2O (M=Co,Ni), having an interesting pillared layer structure, were found. The molybdates crystallize in the triclinic system with space group P−1, Z=1 with unit cell parameters of a=5.525(3) Å, b=7.058(4) Å, c=7.551(5) Å, α=90.019(10)°, β=105.230(10)°, γ=90.286(10)° for CoMo4O13·2H2O, and a=5.508(2) Å, b=7.017(3) Å, c=7.533(3) Å, α=90.152(6)°, β=105.216(6)°, γ=90.161(6)° for NiMo4O13·2H2O The structure is composed of two-dimensional molybdenum-oxide (2D Mo-O) sheets pillared with CoO6 octahedra. The 2D Mo-O sheet is made up of infinite straight ribbons built up by corner-sharing of four molybdenum octahedra (two MoO6 and two MoO5OH2) sharing edges. These infinite ribbons are similar to the straight ones in triclinic-K2Mo4O13 having 1D chain structure, but are linked one after another by corner-sharing to form a 2D sheet structure, like the twisted ribbons in BaMo4O13·2H2O (or in orthorhombic-K2Mo4O13) are. 相似文献
8.
Maravanji S. Balakrishna P. Chandrasekaran Ramalingam Venkateswaran 《Journal of organometallic chemistry》2007,692(13):2642-2648
Cyclodiphosphazanes having donor functionalities such as cis-[tBuNP(OR)]2 (R = C6H4OMe-o (2); R = CH2CH2OMe (3); R = CH2CH2SMe (4); R = CH2CH2NMe2 (5)) were obtained in good yield by reacting cis-[tBuNPCl]2 (1) with corresponding nucleophiles. The reactions of 2-5 with [RuCl2(η6-cymene)]2, [MCl(COD)]2 (M = Rh, Ir), [PdCl2(PEt3)]2 and [MCl2(COD)] (M=Pd, Pt) result in the formation of exclusively monocoordinated mononuclear complexes of the type cis-[{tBuNP(OR)}2MLn-κP] irrespective of the reaction stoichiometry and the reaction conditions. In contrast, 2-5 react with [RhCl(CO)2]2, [PdCl(η3-C3H5)]2, CuX (X=Cl, Br, I) to give homobinuclear complexes. Interestingly, CuX produces both mono and binuclear complexes depending on the stoichiometry of the reactants and the reaction conditions. The mononuclear complexes on treatment with appropriate metal reagents furnish heterometallic complexes. 相似文献
9.
Stefan Köcher Gerard P.M. van Klink Gerard van Koten Heinrich Lang 《Journal of organometallic chemistry》2006,691(19):3955-3961
Ferrocene-bridged NCN pincer complexes of structural type Fe(η5-C5H4-4-NCN-1-MX)2 (X = I: 6, M = Pd; 7, M = Pt; X = Cl: 8, M = Pt; NCN = [4-C6H2(CH2NMe2)2-2,6]−) are accessible by the subsequent reaction of Fe(η5-C5H4-4-NCNH)2 (4) with nBuLi and [PtCl2(SEt2)2] (synthesis of 8) or treatment of Fe(η5-C5H4-4-NCN-1-I)2 (5) with [Pd2(dba)3] (synthesis of 6) or [Pt(tol)2(SEt2)]2 (synthesis of 7) (dba = dibenzylidene acetone, tol = 4-tolyl). In addition, the Sonogashira cross-coupling of Fe(η5-C5H4I)2 (1) with HCC-4-NCNH (2) gives Fe(η5-C5H4-CC-4-NCNH)2 (3). The reaction behavior of 3 towards tBuLi is reported as well.Cyclovoltammetric studies show that the ferrocene entity can be oxidized reversibly. The Fe(II)/Fe(III) potential decreases with increasing electron density at the NCN pincer units due to the presence of the M-halide moiety (M = Pd, Pt).The solid state structure of Fe(η5-C5H4-4-NCN-1-PdI)2 (6) is presented. In 6 the Fe(η5-C5H4)2 unit connects two NCN-PdI pincer entities with palladium in a square-planar environment. The cyclopentadienyl ligands show a staggered conformation. The C6H2 rings are tilted by 23.5(3)° towards the C5H4 entities and the C6H2 plane is almost coplanar with the coordination plane (10.3(3)°). 相似文献
10.
The rare-earth dicarboxylate hybrid materials [Ce(H2O)]2[O2C(CH2)2CO2]3 ([Ce(Suc)]) and [Sm(H2O)]2[O2C(CH2)2CO2]3·H2O ([Sm(Suc)]) have been hydrothermally synthesized (200°C, 3 days) under autogenus pressure. [Ce(Suc)] is triclinic, a=7.961 (3) Å, b=8.176 (5) Å, c=14.32 (2) Å, α=97.07° (7), β=96.75° (8), γ=103.73° (6), and z=2. The crystal structure of this compound has been determined using 3120 unique single crystal data. The final refinements let the agreement factors R1 and wR2(F2) converge to 0.0138 and 0.0363, respectively. [Ce(Suc)] is built up from infinite chains of edge-sharing nine-fold coordinated cerium atoms running along [100]. These chains are interconnected by the carbon atoms of the succinate anions, leading to a three-dimensional hybrid framework. The cell constants of [Sm(Suc)], isotypic with monoclinic C2/c [Pr(H2O)]2[O2C(CH2)2CO2]3·H2O ([Pr(Suc)]), were refined starting from X-ray powder data: a=20.275 (3) Å, b=7.919 (6) Å, c=14.130 (3) Å, and β=121.45° (1). Despite its lower symmetry, [Ce(Suc)] presents an important structural filiation with [Sm(Suc)] 相似文献
11.
Phase transitions in MgAl2O4 were examined at 21-27 GPa and 1400-2500 °C using a multianvil apparatus. A mixture of MgO and Al2O3 corundum that are high-pressure dissociation products of MgAl2O4 spinel combines into calcium-ferrite type MgAl2O4 at 26-27 GPa and 1400-2000 °C. At temperature above 2000 °C at pressure below 25.5 GPa, a mixture of Al2O3 corundum and a new phase with Mg2Al2O5 composition is stable. The transition boundary between the two fields has a strongly negative pressure-temperature slope. Structure analysis and Rietveld refinement on the basis of the powder X-ray diffraction profile of the Mg2Al2O5 phase indicated that the phase represented a new structure type with orthorhombic symmetry (Pbam), and the lattice parameters were determined as a=9.3710(6) Å, b=12.1952(6) Å, c=2.7916(2) Å, V=319.03(3) Å3, Z=4. The structure consists of edge-sharing and corner-sharing (Mg, Al)O6 octahedra, and contains chains of edge-sharing octahedra running along the c-axis. A part of Mg atoms are accommodated in six-coordinated trigonal prism sites in tunnels surrounded by the chains of edge-sharing (Mg, Al)O6 octahedra. The structure is related with that of ludwigite (Mg, Fe2+)2(Fe3+, Al)(BO3)O2. The molar volume of the Mg2Al2O5 phase is smaller by 0.18% than sum of molar volumes of 2MgO and Al2O3 corundum. High-pressure dissociation to the mixture of corundum-type phase and the phase with ludwigite-related structure has been found only in MgAl2O4 among various A2+B3+2O4 compounds. 相似文献
12.
The new nickel selenite chloride, Ni5(SeO3)4Cl2, was obtained by high-temperature solid state reaction of NiCl2, Ni2O3 and SeO2 in a 1:2:4 molar ratio at 700 °C in an evacuated quartz tube. Its structure was established by single-crystal X-ray diffraction. Ni5(SeO3)4Cl2 crystallizes in the triclinic system, space group P-1 (No. 2) with cell parameters of a=8.076(2), b=9.288(2), c=9.376(2) Å, α=101.97(3), β=105.60(3), γ=91.83(3)° and Z=2. All nickel(II) ions in Ni5(SeO3)4Cl2 are octahedrally coordinated by selenite oxygens or/and chloride anions (([Ni(1)O5Cl], [Ni(2)O4Cl2], [Ni(3)O5Cl], [Ni(4)O6] and [Ni(5)O4Cl]). The structure of the title compound features a condensed three-dimensional (3D) network built by Ni(II) ions interconnected by SeO32− anions as well as Cl− anions. Magnetic property measurements show strong antiferromagnetic interaction between nickel(II) ions. 相似文献
13.
Siyabonga Ngubane Susan Jagner Akella Sivaramakrishna 《Journal of organometallic chemistry》2008,693(2):343-348
The synthesis of the new cyclopentadiene, C5Me4(hex)H is described and its reaction with Ru3(CO)12 to yield (C5Me4hex)2Ru2(CO)4 (hex = n-hexyl) is reported. The X-ray crystal structure of the dimer confirms the structure with bridging and terminal CO groups. Reactions of the dimer to yield (C5Me4hex)Ru(CO)2X (X = Cl, Br, I) are reported. IR, NMR and mass spectra are reported for all new compounds. The solubility of the dimer is found to be 10 times greater than that for (C5Me5)2Ru2(CO)4. 相似文献
14.
Two new alkali uranyl oxychloro vanadates M7(UO2)8(VO4)2O8Cl with M=Rb, Cs, have been synthesized by solid-state reactions and their structures determined from single-crystal X-ray diffraction data. They crystallize in the orthorhombic system with space groups Pmcn and Pmmn, respectively. The a and b unit cell parameters are almost identical in both compounds while the c parameter in the Rb compound is doubled: Rb—a=21.427(5) Å, b=11.814(3) Å, c=14.203(3) Å, V=3595.1(1) Å3, Z=4, ρmes=5.93(2) g/cm3, ρcal=5.82(1) g/cm3; Cs—a=21.458(3) Å, b=11.773(2) Å, c=7.495(1) Å, V=1893.6(5) Å3, Z=2, ρmes=6.09(2) g/cm3, ρcal=6.11(1) g/cm3. A full-matrix least-squares refinement yielded R1=0.0221, wR2=0.0562 for 2675 independent reflections and R1=0.0386, wR2=0.1042 for 2446 independent reflections, for the Rb and Cs compounds, respectively. Data were collected with Mo(Kα) radiation and a charge coupled device (CCD) detector of a Bruker diffractometer. Both structures are characterized by [(UO2)8(VO4)2O8Cl]n7n− layers parallel to the (001) plane. The layers are built up from VO4 tetrahedra, UO7 and UO6Cl pentagonal bipyramids, and UO6 distorded octahedra. The UO7 and UO6Cl pentagonal bipyramids are associated by sharing opposite equatorial edges to form infinite chains (UO5-UO4Cl-UO5)n parallel to the a axis. These chains are linked together by VO4 tetrahedra, UO6 octahedra, UO7 corner sharing and UO6Cl, Cl sharing. Both structures differ simply by the symmetry of the layers. The unit cell contains one centrosymmetric layer in the Cs compound, whereas in the two-layer unit cell of the Rb compound, two non-centrosymmetric consecutive layers are related by an inversion center. The layers appear to be held together by the alkali ions. The mobility of the M+ ions within the interlayer space in M7(UO2)8(VO4)2O8Cl and carnotite analog compounds is compared. 相似文献
15.
Sofia I. Pascu Karl S. Coleman Nicholas H. Rees 《Journal of organometallic chemistry》2005,690(6):1645-1658
Treatment of the bulky iminophosphine ligand [Ph2PCH2C(Ph)N(2,6-Me2C6H3)] (L) with [M(CH3CN)2(ligand)]+n, where for M = Pd(II): ligand = η3-allyl, n = 1, and for M = Rh(I), ligand: 2(C2H4), 2(CO) or cod, n = 0, yields the mono-cationic iminophosphine complexes [Pd(η3-C3H5)(L)][BF4] (1), [Rh(cod)(L)][BF4] (2), [Rh(CO)(CH3CN)(L)][BF4] (3), and cis-[Rh(L)2][BF4] (4). All the new complexes have been characterised by NMR spectroscopy and X-ray diffraction. Complex 1 shows moderate activity in the copolymerisation of CO and ethene but is inactive towards Heck coupling of 4-bromoacetophenone and n-butyl acrylate. 相似文献
16.
Manoj K. Pal Amey P. Wadawale Vimal K. Jain Edward R.T. Tiekink 《Journal of organometallic chemistry》2007,692(20):4237-4243
The reaction of triorgano-gallium and -indium etherate with heterocyclic carboxylic acids in benzene at room temperature yields complexes of the type [R2M(L)]n(M = Ga or In; R = Me or Et; L = 2-(C5H4N)CO2, 2-(C4H3N2)CO2 or 2-(C9H6N)CO2). These complexes have been characterized by elemental analysis, IR, UV-vis, NMR (1H and 13C{1H}) and mass spectral data. Complexes with L = (C5H4N)CO2- and (C9H6N)CO2- showed photoluminescence on excitation with ∼250 or ∼310 nm radiation, respectively. Single crystal X-ray structural analysis of [Me2M(O2C-C5H4N-2)]2 (M = Ga or In), revealed a dimeric structure with five-coordinate metal atoms arising from the presence of two tridentate bridging picolinate ligands. 相似文献
17.
An investigation into the effect of the flexibility of substituents on the disorder of the Cl-Rh-CO moiety in Vaska-type trans-[Rh(CO)Cl(PR3)2] complexes is presented. The influence of the packing of the complexes with PR3 = P(CH2C6H5)3, P(OC6H5)3, P(O-2-MeC6H4)3 and P(O-2,6-Me2C6H3)3 was evaluated by comparing the X-ray structures with the results of DFT calculations on these complexes. Reasonable agreement between the calculated and molecular structures was found. A good agreement, however, was found between the calculated and crystallographic structures when comparing the coordination polyhedron around the Rh atom. The main difference between the calculated and solid state structures appeared to be in the orientation of the phenyl groups of the P-donor ligands. 相似文献
18.
The synthesis, derivatization and coordination behavior of a new aminobis(diphosphonite), PhN{P(OC6H4OMe-o)2}2 (1) is described. The ligand 1 reacts with H2O2, elemental sulfur or selenium to give the corresponding dichalcogenides PhN{P(E)(OC6H4OMe-o)2}2 (E = O, 2; S, 3; Se, 4) in good yield. Reactions of 1 with Mo(CO)6, Pd(NCCH3)2Cl2 and Pt(COD)Cl2 resulted in the formation of the chelate complexes, Mo(CO)4[PhN{P(OC6H4OMe-o)2}2] (5) and MCl2[PhN{P(OC6H4OMe-o)2}2] (M = Pd,7; M = Pt, 8) whereas in the reaction of 1 with [CpFe(CO)2]2, one of the P-N bonds cleaves due to the metal assisted hydrolysis to give a mononuclear complex, [CpFe(CO){P(O)(OC6H4OMe-o)2}{PhN(H)(P(OC6H4OMe-o)2)}] (6). The molecular structures of 1, 4, 5 and 6 are determined by X-ray studies. 相似文献
19.
M. Harcharras H. Assaaoudi V. D’Orazio F. Capitelli 《Journal of solid state chemistry》2003,172(1):160-165
A tetrasodium dimagnesium dihydrogen diphosphate octahydrate Na4Mg2(H2P2O7)4·8H2O was synthesized. It crystallizes in the monoclinic system, space group P21/m (no. 11), Z=4, and its unit-cell parameters are: a=8.0445(3) Å, b=11.5244(5) Å, c=9.0825(4) Å, β=113.1401(2)°, V=774.28(6) Å3. The structure was determined by single-crystal X-ray diffractometry and refined to a R index of 0.0294 (wR=0.0727) for 1878 independent reflections with I>2σ(I). The framework is made by the alternance of layers of MgO6/NaO6 octahedra and double tetrahedra PO4 along b-axis. Such layers are characterized by the presence of strong hydrogen bonds. (H2P2O7)2− anions exhibit bent eclipsed conformation. Besides, the crystal was analyzed by FT-IR and micro-Raman vibrational spectroscopy. No coincidences of the majority of the Raman and infrared spectra bands of Na4Mg2(H2P2O7)4·8H2O confirms a centrosymmetric structure of this material. The vibrational spectra confirm the bent POP configuration in this compound. 相似文献
20.
Maria Agostina Cinellu Fabio Cocco Sergio Stoccoro Mario Manassero 《Journal of organometallic chemistry》2009,694(18):2949-47
Reaction of Na[AuCl4] with 2-vinylpyridine (vinpy) and 2-ethylpyridine (etpy) affords the N-bonded adducts Au(Rpy)Cl3 (R = CH2CH, vinpy; CH3CH2, etpy). Cationic adducts, [Au(vinpy)2Cl][X]2 (X = BF4, PF6) and [Au(etpy)2Cl2][BF4], were also obtained by reaction of Au(Rpy)Cl3 with Rpy (1:1) and excess NaBF4 or KPF6. Thermal activation of Au(vinpy)Cl3 in water gives the five-membered cycloaurated derivative [Au(k2-C,N-CH2CH(Cl)-C5H4N)Cl2] formally resulting through a trans nucleophilic addition of a chloride onto the CC bond. No cyclometallated derivatives are obtained by reactions of Au(etpy)Cl3. An X-ray crystal structure determination on the PPh3 derivative [Au(k2-C,N-CH2CH(Cl)-C5H4N)(PPh3)Cl][PF6] was carried out. 相似文献