Direct synthesis of dimethyl carbonate from methanol and carbon dioxide over CeO2(X)-ZnO(1-X) nano-catalysts.

CeO2(X)-ZnO(1-X) (X = 0, 0.1, 0.3, 0.5, 0.7, 0.9, and 1.0) nano-catalysts were prepared by a co-precipitation method with a variation of CeO2 content (X, mol%), and they were applied to the direct synthesis of dimethyl carbonate from methanol and carbon dioxide. Successful formation of CeO2(X)-ZnO(1-X) nano-catalysts was well confirmed by XRD analysis. The amount of DMC produced over CeO2(X)-ZnO(1-X) catalysts exhibited a volcano-shaped curve with respect to CeO2 content. Acidity and basicity of CeO2(X)-ZnO(1-X) nano-catalysts were measured by NH3-TPD and CO2-TPD experiments, respectively, to elucidate the effect of acidity and basicity on the catalytic performance in the reaction. It was revealed that the catalytic performance of CeO2(X)-ZnO(1-X) nano-catalysts was closely related to the acidity and basicity of the catalysts. Amount of dimethyl carbonate increased with increasing both acidity and basicity of the catalysts. Among the catalysts tested, CeO2(0.7)-ZnO(0.3) with the largest acidity and basicity showed the best catalytic performance in the direct synthesis of dimethyl carbonate from methanol and carbon dioxide.

Hg(II)...Pd(II) metallophilic interactions.

Reaction of bis(pentafluorophenyl)mercury (1) with the Pd(II) complexes [Pd(salophen)] (I, salophen = N,N'-disalicylidene-o-phenylenediaminate) and [Pd(N--C)(OAc)]2 (II, N--C = (2-(2-pyridyl)phenyl-C,N)) leads to the formation of the supramolecular complexes [1-(I)2] and [1-(II)2] in which the mercury synthon is sandwiched by two molecules of the palladium complex. These complexes, whose formation can be observed in solution by UV-vis spectroscopy, have been fully characterized. The short Hg-Pd distances of 3.2841(2) A in [1-(I)2] and 3.1065(8) A in [1-(II)2] indicate the presence of a Hg-Pd metallophilic interaction which, at least for [1-(II)2], is complemented by a Pd(II)-->Hg(II) donor-or component.

[Re6Te8(CN)6][(Ir(CO)(PPh3)2)6](OTf)2 : a new Re6 cluster-supported iridium(I) compound.

A new hexanuclear rhenium cluster encapsulated by six iridium complexes, [Re6Te8(CN)6][(Ir(CO)(PPh3)2)6](OTf)2 (3), which is effective in catalyzing the hydrogenation of p-CH3C6H4C[triple bond]CH to p-CH3C6H4CH=CH2 has been prepared.

Synthesis and anion affinity of a bidendate sulfonium fluorosilane Lewis acid.

The cationic fluorosilane [1-Ant(2)FSi-2-Me(2)S-(C(6)H(4))](+) (2(+)) readily complexes fluoride ions to afford the corresponding zwitterionic difluorosilicate complex 1-Ant(2)F(2)Si-2-Me(2)S-(C(6)H(4)) (2-F) with a binding constant in CHCl(3) of 7 (+/-1) x 10(6) M(-1). Structural and computational results indicate that the high fluorophilicity of 2(+) arises from both Coulombic and cooperative effects reflected by the formation of a Si-F-->S bridge with a F-->S distance of 2.741(3) A.

Remarkably efficient hydrolysis of methylparathion catalyzed by [2-(2-pyridyl)phenyl-C,N]palladium(II) complexes.

The reaction of the palladium(II) acetate derivative [Pd(NwedgeC)(OAc)]2 (NwedgeC = (NC5H4-2-C6H4(C2,N) or (2-(2-pyridyl)-phenyl-C,N)) with methylparathion and water in THF leads to the formation of [Pd(NwedgeC)(mu-SP(=O)(OCH3)2)]2 (1), which reacts with PPh3 in THF to afford mononuclear complex [Pd(NwedgeC)(SP(=O)(OCH3)2)(PPh3)] (2). Compounds 1 and 2 have been characterized by 1H, 13C, and 31P NMR spectroscopy; elemental analysis; and single-crystal X-ray diffraction. When dissolved in water, 1 serves as a precatalyst for the hydrolysis of methylparathion. Kinetic and spectroscopic studies suggest that compound 1 dissociates in aqueous solution to afford cationic diaqua complex [Pd(NwedgeC)(OH2)2]+ (A). At basic pH, A is converted into its deprotonated form [Pd(NwedgeC)(OH2)(OH)] (B), which dimerizes to afford a dinuclear complex, presumably [Pd(NwedgeC)(mu-OH)]2 (C). At pH 7, the reaction is first order in substrate and first order in palladium catalyst A, with k2 = 146 +/- 9 M(-1) s(-1) at 303 K. At more-basic pH, the reaction rate increases and shows an apparent half-order dependence in palladium catalyst. These observations suggest that the active form of the catalyst at basic pH is B, whose concentration is controlled by an equilibrium with inactive C. Analysis of the data obtained at pH 9 yields a dimer formation constant K(f) = [C]/[B]2 = (6.6 +/- 5.6) x 10(6) M(-1) and a second-order rate constant k2 of (8.6 +/- 3.6) x 10(3) M(-1) s(-1) at 298 K. The pH dependence of the reaction rate as well as a spectroscopic titration indicates that the pKa of A is in the 9.5-9.7 range. Determination of the activation parameters at both pH 7 and 9 suggests that catalysis occurs via an associative mechanism whose rate-determining step involves the substitution of a water ligand of A by a molecule of methylparathion at neutral pH and nucleophilic attack of the phosphorus center of methylparathion by a hydroxide ligand of B at basic pH.

Stoichiometric reactions of methylparathion with a palladium aryl oxime metallacycle.

The reaction of [Pd(3)(OAc)(6)] with (E)-acetophenone oxime and pyridine in CHCl(3) under reflux affords the metallacycle [Pd(OAc)[C,N-(C(6)H(4)C(CH(3))=NOH)-2](py)] (1) as a yellow air-stable complex. The same reaction carried out at room temperature in the absence of pyridine affords the trinuclear oximato complex [Pd(mu-(E)-ON=C(CH(3))Ph)(mu-OAc)](3) (2), which can be converted into 1 upon heating in the presence of pyridine. As indicated by (1)H and (31)P NMR spectroscopy, complex 1 reacts with methylparathion in acetone-d(6)-D(2)O solutions to afford [Pd(SP(=O)(OCH(3))(2))[C,N-(C(6)H(4)C(CH(3))=NOH)-2](py)] (3) and [Pd(mu-SP(=O)(OCH(3))(2))[C,N-(C(6)H(4)C(CH(3))=NOH)-2]](2) (4) as well as free p-nitrophenol. Compounds 1-4 have been characterized by single-crystal X-ray analysis, NMR and EA. Compounds 1 and 3 are mononuclear complexes with the acetate and dimethylthiophosphate ligand, respectively, trans from the phenyl group. Compound 2 is a trinuclear complex whose structure can be derived from that of [Pd(3)(OAc)(6)] by replacing three of the acetate ligands on one side of Pd(3) plane by three N,O-coordinated oximate ligands. Complex 4 is a dinuclear complex in which the two square-planar palladium moieties are linked by the sulfur atoms of the bridging dimethylthiophosphate ligands.

Carbon-carbon bond formation involving reactions of alkynes with group 9 metals (Ir, Rh, Co): preparation of conjugated olefins.

Stable alkynyl complexes of iridium(III) (L(n)Ir-triple bond-R) that are prepared from the reactions of terminal alkynes readily undergo the intramolecular C-C bond-forming reactions between the alkynyl and adjacent hydrocarbyl ligands to yield conjugated olefins. These reactions are initiated by electrophiles (H(+), Me(+)) that attack the beta carbon of the alkynyl ligand to increase the electrophilicity of the alpha carbon of the alkynyl ligand. The C-C bond is then formed between the alpha carbons of the alkynyl and adjacent hydrocarbyl ligands.