Characterization studies of 1-(4-cyano-2-oxo-1,2-dihydro-1-pyridyl)-3-(4-cyano-1,2-dihydro-1-pyridyl)propane formed from the reaction of hydroxide Ion with 1,3-Bis-(4-cyano pyridinium)propane

The aqueous alkaline reaction of 1,3-bis(4-cyanopyridinium)propane dibromide, a reactant constituted of two pyridinium rings linked by a three-methylene bridge, generates a novel compound,1 -(4-cyano-2-oxo-1,2-dihydro-1-pyridyl)-3-(4-cyano-1,2-dihydro-1-pyridyl)propane. The reaction pathway is attributed to the proximity of the OH- ion inserted between two pyridinium moieties, which occurs only in bis(pyridinium) derivatives connected by short methylene spacers, where charge-conformational effects are important.

cis-Bis{1,1-dibenzyl-3-[(furan-2-yl)carbonyl]thioureato-kappa 2 O,S}nickel(II)

In the title compound, [Ni(C(20)H(17)N(2)O(2)S)(2)], the NiII atom is coordinated by the S and O atoms of two 1,1-dibenzyl-3-[(furan-2-yl)carbonyl]thioureate ligands in a distorted square-planar geometry. The two O and two S atoms are mutually cis to each other. The Ni-S and Ni-O bond lengths lie within the range of those found in related structures. The dihedral angle between the planes of the two chelating rings is 20.33 (6)degrees.

Bis(tetraphenylphosphonium) tris[N-(methylsulfonyl)dithiocarbimato(2-)-kappa(2)S,S ']stannate(IV)

In the title complex, (C(24)H(20)P)(2)[Sn(C(2)H(3)NO(2)S(3))(3)], the Sn(IV) atom is coordinated by three N-(methylsulfonyl) dithiocarbimate bidentate ligands through the anionic S atoms in a slightly distorted octahedral coordination geometry. There is one half-molecule in the asymmetric unit; the complex is located on a crystallographic twofold rotation axis passing through the cation and bisecting one of the (non-symmetric) ligands, which appears thus disordered over two sites of equal occupancy. In the crystal structure, weak intermolecular C-H center dot center dot center dot O and C-H center dot center dot center dot S interactions contribute to the packing stabilization.

cis-Bis[1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureato-kappa(2)O,S]copper(II)

In the title compound, [Cu(C(20)H(17)N(2)O(2)S)(2)], the Cu(II) atom is coordinated by the S and O atoms of two 1,1-dibenzyl-3-(furan-2-ylcarbonyl)thioureate ligands in a distorted square-planar geometry. The two O and two S atoms are mutually cis to each other. The Cu-S and Cu-O bond lengths lie within the ranges of those found in related structures. The dihedral angle between the planes of the two chelating rings is 26.15 (6)degrees.

cis-Bis[N-(2-furoyl)-N ',N '-diphenylthioureato-kappa(2)O,S]nickel(II)

In the title compound, [Ni(C(18)H(13)N(2)O(2)S)(2)], the Ni(II) atom is coordinated by the S and O atoms of two N-furoyl-N ',N '-diphenylthioureate ligands in a slightly distorted squareplanar coordination geometry. The two O and two S atoms are cis to each other.

cis-bis(N-benzoyl-N ',N '-dibenzylthio-ureato-kappa O-2,S)nickel(II)

In the title compound, [Ni(C22H19N2OS)(2)], the Ni-II atom is coordinated by the S and O atoms of two N-benzoyl-N',N'-dibenzylthioureate ligands in a slightly distorted square-planar geometry. The two O atoms are cis, as are the two S atoms.

3,3-Bis[(4-chlorophenyl)sulfanyl]-1-methylpiperidin-2-one

The piperidone ring in the title compound, C(18)H(17)Cl(2)NOS(2), has a distorted half-chair conformation. The S-bound benzene rings are approximately perpendicular to and splayed out of the mean plane through the piperidone ring [dihedral angles = 71.86 (13) and 46.94 (11)degrees]. In the crystal, C-H center dot center dot center dot O interactions link the molecules into [010] supramolecular chains with a helical topology. C-H center dot center dot center dot Cl and C-H center dot center dot center dot pi interactions are also present.

5-Methyl-2,4-bis(methylsulfanyl)tricyclo[6.2.1.0(2,7)]undeca-4,9-diene-3,6-dione

The structure analysis of the title compound, C(14)H(16)O(2)S(2), shows the SMe and H atoms of the bond linking the six-membered rings to be syn and also to be syn to the bridgehead -CH(2)- group. Each of the five-membered rings adopts an envelope conformation at the bridgehead -CH(2)- group. The dione-substituted ring adopts a folded conformation about the 1,4-C center dot center dot center dot C vector, with the ketone groups lying to one side. The cyclohexene ring adopts a boat conformation.

Crystal structure of 1,2-bis(4-fluoro-2-methylphenyl)ditelluride, [Te(C7H6F)](2)

C14H12F2Te2, monoclinic, C12/c1 (no. 15), a = 23.650(2) angstrom, b = 7.792(1) angstrom, c = 7.556(1) angstrom, beta = 106.47(1)degrees, V = 1335.2 angstrom(3), Z = 4, R-gt(F) = 0.041, wR(ref)(F-2) = 0.123, T= 98 K.

One-pot synthesis of mixed (Z)-1,2-bis(organylchalcogene)-1-alkenes precursors of the novel beta-organylthio vinyllithium intermediates

One-pot hydrochalcogenation of 1-phenylthioacetylenes using organylselenolate and organyltellurolate anions generated by the insertions of selenium and tellurium in n-organyl lithium produced (Z)-1,2-bis(organylchalcogene)-1-alkenes. The chemical reactivity of these mixed 1,2-bis(organylchalcogene)-1-alkenes was studied by Te/Li and Se/Li stereoretentive exchanges carried out with n-butyl lithium, furnishing the new intermediate species (Z)-beta-organylthio vinyllithium anions, which were trapped with aldehydes, to give the (Z)-3-hydroxy vinyl thioethers with total control of the regio- and stereochemistry. (c) 2010 Elsevier Ltd. All rights reserved.

Large-N solutions of the Heisenberg and Hubbard-Heisenberg models on the anisotropic triangular lattice: application to Cs2CuCl4 and to the layered organic superconductors kappa-(BEDT-TTF)(2)X (BEDT-TTF bis(ethylene-dithio)tetrathiafulvalene); X anion)

We solve the Sp(N) Heisenberg and SU(N) Hubbard-Heisenberg models on the anisotropic triangular lattice in the large-N limit. These two models may describe respectively the magnetic and electronic properties of the family of layered organic materials K-(BEDT-TTF)(2)X, The Heisenberg model is also relevant to the frustrated antiferromagnet, Cs2CuCl4. We find rich phase diagrams for each model. The Sp(N) :antiferromagnet is shown to have five different phases as a function of the size of the spin and the degree of anisotropy of the triangular lattice. The effects of fluctuations at finite N are also discussed. For parameters relevant to Cs2CuCl4 the ground state either exhibits incommensurate spin order, or is in a quantum disordered phase with deconfined spin-1/2 excitations and topological order. The SU(N) Hubbard-Heisenberg model exhibits an insulating dimer phase, an insulating box phase, a semi-metallic staggered flux phase (SFP), and a metallic uniform phase. The uniform and SFP phases exhibit a pseudogap, A metal-insulator transition occurs at intermediate values of the interaction strength.

Hydrolytic kinetic resolution of terminal mono- and bis-epoxides in the synthesis of insect pheromones: routes to (-)-(R)- and (+)-(S)-10-methyldodecyl acetate, (-)-(R)-10-methyl-2-tridecanone, (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol), (-)-(1R,7R)-1,7-dime

Hydrolytic kinetic resolution (HKR) of functionalised epoxides using (salen)Co(OAc) complexes provides enantiomerically enriched epoxides and diols, which have been transformed into important insect sex pheromones. In this general approach, (-)-(R)- and (+)-(S)-10-methyldodecyl acetates from the smaller tea tortrix moth were obtained, as was (-)-(R)-10-methyltridecan-2-one from the southern corn rootworm. The (S)-epoxide obtained from undec-1-en-6-yne was transformed to (-)-(R)-(Z)-undec-6-en-2-ol (Nostrenol) from ant-lions. HKR of appropriate bisepoxides was also investigated, and transformations of the resulting bisepoxides and epoxydiols provided (-)-(1R,7R)-1,7-dimethylnonylpropanoate from corn rootworms, (-)-(6R,12R)-6,12-dimethylpentadecan-2-one from the female banded cucumber beetle, and (-)-(2S,11S)-2,11-diacetoxytridecane and (+)-(2S,12S)-2,12-diacetoxytridecane from female pea-midges. (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis and characterization of mono- and bis-ligand zinc(II) and cadmium(II) complexes of the di-2-pyridylketone Schiff base of S-benzyl dithiocarbazate (Hdpksbz) and the X-ray crystal structures of the [Zn(dpksbz)2] and [Cd(dpksbz)NCS]2 complexes

New mono- and bis-chelated zinc(II) and cadmium(II) complexes of formula, [M(dpksbz)NCS] (dpksbz = anionic form of the di-2-pyridylketone Schiff base of S-benzyldithiocarbazate) and [M(dpksbz)(2)] (M = Zn-II, Cd-II) have been prepared and characterized. The structure of the bis-ligand complex, [Zn(dpksbZ)(2)] has been determined by X-ray diffraction. The complex has a distorted octahedral geometry in which the ligands are coordinated to the zinc(II) ion as uninegatively charged tridentate chelates via the thiolate sulfur atoms, the azomethine nitrogen atoms and the pyridine nitrogen atoms. The distortion from a regular octahedral geometry is attributed to the restricted bite angles of the Schiff base ligands. X-ray structural analysis shows that the [Cd(dpksbz)NCS](2) complex is a centrosymmetric dimer in which each of the cadmium(II) ions adopts a five-coordinate, approximately square-pyramidal configuration with the Schiff base acting as a tetradentate chelating agent coordinating a cadmium(II) ion via one of the pyridine nitrogen atoms, the azomethine nitrogen atom and the thiolate sulfur atom; the second pyridine nitrogen atom is coordinated to the other cadmium(II) ion of the dimer. The fifth coordination position around each cadmium(II) is occupied by an N-bonded thiocyanate ligand. (C) 2003 Elsevier Science Ltd. All rights reserved.

Copper(II) aza-bis(oxazoline) complex immobilized onto ITQ-2 and MCM-22 based materials as heterogeneous catalysts for the cyclopropanation of styrene

A copper(II) chiral aza-bis(oxazoline) homogeneous catalyst (CuazaBox) was anchored onto the external surface of MCM-22 and ITQ-2 structures, as well as encapsulated into hierarchical MCM-22. The transition metal complex loading onto the porous solids was determined by ICP-AES and the materials were also characterized by elemental analysis (C, N, H, S), FTIR, XPS, TG and low temperature N-2 adsorption isotherms. The materials were tested as heterogeneous catalysts in the benchmark reaction of cyclopropanation of styrene to check the effect of the immobilization procedure on the catalytic parameters, as well as on their reutilization in several catalytic cycles. Catalyst CuazaBox anchored onto the external surface of MCM-22 and ITQ-2 materials were more active and enantioselective in the cyclopropanation of styrene than the corresponding homogeneous phase reaction run under similar experimental conditions. This is due to the propylation of the acidic aza-Box nitrogen. HMCM-22 was nevertheless the best heterogeneous catalyst. Encapsulation of CuazaBox on post-synthesis modified MCM-22 materials led to low activities and enantioselectivities. But reversal on the stereochemical course of the reaction was observed, probably due to confinement effect. (C) 2013 Elsevier Inc. All rights reserved.