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61.
This article describes the structure determination of five homoleptic d(10) metal-aryl/alkylacetylides [RC triple bond CM] (M=Cu, R=tBu 1, nPr 2, Ph 3; R=Ph, M=Ag 4; Au 5) by using X-ray single-crystal and powder diffraction. Complex 1.C6H6 reveals an unusual Cu20 catenane cluster structure that has various types of tBuC triple bond C-->Cu coordination modes. By using this single-crystal structure as a starting model for subsequent Rietveld refinement of X-ray powder diffraction data, the structure of the powder synthesized from CuI and tBuC triple bond CH was found to have the same structure as 1. Complex 2 has an extended sheet structure consisting of discrete zig-zag Cu4 subunits connected through bridging nPrC triple bond C groups. Complex 3 forms an infinite chain structure with extended Cu-Cu ladders (Cu-Cu=2.49(4)-2.83(2) A). The silver(I) congener 4 is iso-structural to 3 (average Ag-Ag distance 3.11 A), whereas the gold(I) analogue 5 forms a Au...Au honeycomb network with PhC triple bond C pillars (Au-Au=2.98(1)-3.26(1) A). Solid-state properties including photoluminescence, nu(C triple bond C) stretching frequencies and thermal stability of these polymeric systems are discussed in the context of the determined structures. 相似文献
62.
63.
Beltrami I Bylsma BG DeBonte R Gan KK Koltick D Loeffler FJ Low EH McIlwain RL Miller DH Ng CR Ong PP Rangan LK Shibata EI Wilson RJ Derrick M Fernandez E Fries R Hyman L Kooijman P Loos JS Musgrave B Price LE Schlereth J Sugano K Weiss JM Wood DE Baranko G Baringer P Blockus D Brabson B Forden GE Gray SW Jung C Neal H Ogren H Rust DR Valdata-Nappi M Akerlof C Bonvicini G Chapman J Errede D Harnew N Kesten P Kooijman S Meyer DI Nitz D Rubin D Seidl AA Thun R Trinko T Willutzky W Cork B Keller L 《Physical review letters》1985,54(16):1775-1778
64.
Winghong Chan Suei Yee Lam-Leung Chingfai Ng Junqi Ding Shiping Xi 《Journal of polymer science. Part A, Polymer chemistry》1995,33(15):2525-2531
New diamino monomers IIa – IIg were synthesized in a two-step reaction sequence starting from p-acetamidobenzenesulfonyl chloride. Solution polymerization of these monomers in DMAC with terephthaloyl or isophthaloyl chloride resulted in the formation of a series of 14 poly(amide sulfonamide)s (PASAs) in excellent yield (> 95%). The polymers have in-trinsic viscosities of 0.32–1.11 dL g?1. Except for polymers IIIa ? p and IIId - p , all other PASAs were readily soluble in aprotic polar solvents including DMAC, DMF, and DMSO. Thermogravimetric analyses of the polymers showed moderate thermal stability with 10% weight loss being recorded in the range of 325–408°C. In addition, these polymers exhibit moderate chemical stabilities toward alkali, acidic, and chromic acid solution. © 1995 John Wiley & Sons, Inc. 相似文献
65.
The phosphapalladacycle derived from 1-(2',5'-dimethylphenyl)ethyldiphenylphosphine has been prepared in the optically active and racemic forms. The phosphine was synthesized as a racemate by the treatment of 1-chloro-1-(2',5'-dimethylphenyl)ethane with sodium diphenylphosphide in THF. The racemic phosphapalladacycle was subsequently obtained as the chloro-bridged dimer by the treatment of the phosphine with palladium(II) acetate followed by anion metathesis with lithium chloride. Alternatively, the phosphine could be optically resolved via metal complexation using (R,R)-bis(mu-chloro)bis{1-[1-(N,N-dimethylamino)ethyl]naphthyl-C(2),N}dipalladium(II) as the resolving agent. An efficient separation of the resulting diastereomeric complexes was achieved by silica gel chromatography. The obtained optically resolved diastereomers were next subject to chemoselective removal of the (R)-N,N-(dimethylamino)-1-(1-naphthyl)ethylaminate auxiliary by treatment with concentrated hydrochloric acid. This process yielded the binuclear dimer complexes containing the resolved eta(1)-P ligand. Cyclopalladation of the coordinated phosphine could next be performed by treatment of its eta(1)-P binuclear dimer with silver(I) hexafluorophosphate(V) in a dichloromethane/water mixture followed by treatment with lithium chloride, giving rise to a pair of optically pure enantiomeric dimers with [alpha](D) -322 and +319 degrees in CH(2)Cl(2). Despite the possibilities of the phosphine to attain a five- membered structure by ortho-palladation or a six-membered ring formation by aliphatic C-H bond activation, only the former was observed. X-ray crystallographic data of the meso dimer and an acetylacetonate derivative indicated that the phosphapalladacycle alpha-C methyl substituent was axially located. The 2-D (1)H-(1)H ROESY spectrum of the acetylacetonate derivative further revealed that the phosphapalladacycle was conformationally rigid in CDCl(3). 相似文献
66.
The reactions of π-cyclopentadienylnickel carbonyl dimer with 3,3,3-trimethylpropynyldiphenylphosphine and phenylethynyldiphenylphosphine are described. The products have been characterized by elemental and mass spectral analysis, infrared and NMR spectroscopy. An acetylene bridged complex (π-C5H5Ni)2Ph2PC2-t-Bu, containing an uncoordinated phosphorus atom, has been prepared. The complex can be oxidized to the phosphine oxide derivative (π-C5H5Ni)2Ph2P(O)C2-t-Bu and converted to the phosphonium salts with methyl iodide or ethyl bromide. These are the first reported π-complexes of phosphonium salts. The complex (π-C5H5Ni)2Ph2PC2-t-Bu forms the novel mixed metal derivative [PdCl2][(π-C5H5Ni)2Ph2PC2-t-Bu]2 from bis(benzonitrile)-palladium dichloride. The dicarbonyl complexes Ni(CO)2(Ph2PC2R)2 (R t-Bu, Ph), the phosphine oxide complex (π-C5H5Ni)2(Ph2P(O)C2Ph) and the trinuclear nickel carbonyl derivative Ni(CO)3[(π-C5H5Ni)2Ph2PC2Ph] are described. 相似文献
67.
Four new chiral stationary phases based on mono-(6A-allylcarbamido-6A-deoxy)-arylcarbamoylated β-cyclodextrin were synthesized. The chiral stationary phase of phenylcarbamoylated β-cyclodextrin exhibited excellent separation capability for a variety of chiral compounds. Compared with the previous work, it was found that the spacer remained on the surface of the silica gel and decreased the enantioseparation capability. 相似文献
68.
Experimental data on initial hydrate formation conditions have been obtained for the nitrogen-propane-water system in the L1HG, L1L2H, and L1L2HG regions, where L1 is the water rich liquid phase, L2 is the hydrocarbon rich liquid phase, H is the hydrate and the G is the vapor phase. The measurements covered a range of temperatures from about 275 to 293 K and pressures from about 0.3 to 17.0 MPa. The concentrations covered for the L1HG region extended from 0.94 to 75.0 mole percent propane in the gas phase, and for the L1L2H region they extended from 83.1 to 99.0 mole percent in the condensed liquid phase. Four-phase measurements were made at concentrations of propane from 18.1 to 71.1 mole percent in the gas phase.The experimental data were used to find a fitted binary interaction parameter for predicting hydrate formation in systems containing nitrogen and propane. 相似文献
69.
Ming‐Liang Tong Wei Li Xiao‐Ming Chen Shao‐Liang Zheng Seik Weng Ng 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(4):m232-m234
The title compound, [Cu2(C2H3O2)4(C11H9N)2] or [Cu2(MeCO2)4(phpy)2] (phpy is 4‐phenylpyridine), consists of centrosymmetric dimers in which the CuII atoms display a square‐pyramidal CuO4N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions. 相似文献
70.
Gas-phase activation energies were calculated for three lithium enolate reactions by using several different ab initio and density functional theory (DFT) methods to determine which levels of theory generate acceptable results. The reactions included an aldol-type addition of an enolate to an aldehyde, a proton transfer from an alcohol to a lithium enolate, and an S(N)2 reaction of an enolate with chloromethane. For each reaction, the calculations were performed for both the monomeric and dimeric forms of the lithium enolate. It was found that transition state geometry optimization with B3LYP followed by single point MP2 calculations generally provided acceptable results compared to higher level ab initio methods. 相似文献