Oxo ligand functionalization in the uranyl ion (UO22

By fine-tuning the reaction temperature to 5, 15, 30, and 50 °C, respectively, four different complexes, [Cd(HC4O4)2(H2O)4] (1), [Cd4(C4O4)4(H2O)16]•(H2O)2 (2), [Cd(C4O4)(H2O)2] (3), and [Cd(C4O4)(H2O)2] (4), were formed successfully from the identical initial reaction mixture. Moreover, an unprecedented reversible interconversion among the four complexes at the corresponding reaction temperatures mediated by the mother liquor was observed.

Temperature controlled reversible change of the coordination modes of the highly symmetrical multitopic ligand to construct coordination assemblies: experimental and theoretical studies.

Carboxylate covalently modified polyoxometalates: From synthesis, structural diversity to applications

Two nickel(II) complexes of formula (H3dien)2[Ni2(ox)5]·12H2O (1) and [Ni2(dien)2(H2O)2(ox)]Cl2 (2) (dien = diethylenetriamine and ox = oxalate dianion) have been synthesized and characterized by single-crystal X-ray diffraction. 1 crystallizes in the orthorhombic system, space group Abnn, with a = 15.386(4) A, b = 15.710(4) A, c = 17.071(4) A, and Z = 4. 2 crystallizes in the monoclinic system, space group P21/c, with a = 10.579(1) A, b = 7.258(1) A, c = 13.326(1) A, β = 93.52(3)°, and Z = 2. The structures of 1 and 2 consist of dinuclear oxalato-bridged nickel(II) units which contain bidentate oxalate (1) and tridentate dien in the fac-conformation (2) as terminal ligands. Both features, oxalato as a peripheral ligand and dien in the fac-conformation (instead of its usual mer-conformation), are unprecedented in the coordination chemistry of nickel(II). The nickel atom is six-coordinated in both compounds, the chromophores being NiO6 (1) and NiN3O3 (2). The Ni−O(ox) bond distances at the bridge (2.072(4)...

Influence of the Peripheral Ligand Atoms on the Exchange Interaction in Oxalato-Bridged Nickel(II) Complexes: An Orbital Model. Crystal Structures and Magnetic Properties of (H3dien)2[Ni2(ox)5]·12H2O and [Ni2(dien)2(H2O)2(ox)]Cl2

Self-assembly under hydrothermal conditions has been employed to synthesize several novel uranium-containing polymeric materials in the pyridinedicarboxylic acid (pydc) system. Uranium containing coordination polymers were synthesized utilizing 2,3-pyridinedicarboxylic acid (2,3-pydc), 2,4-pyridinedicarboxylic acid (2,4-pydc) and 2,6-pyridinedicarboxylic acid (2,6-pydc) as the organic linker. Furthermore, several bimetallic compounds were also synthesized, U–M–2,6-pydc (M = Cu, Ag, Pb). A new secondary building unit for uranium(VI) compounds has also been realized in compound 4 [(UO2)2(C7H3NO4)(O)(H2O)] through tetramer building units edge shared to form one-dimensional chains. Presented herein will be the syntheses, crystal structures and fluorescent properties of these uranium-containing compounds.

Synthesis, structure and fluorescent studies of novel uranium coordination polymers in the pyridinedicarboxylic acid system

Reactions of Uranyl Thiolate Complexes with Molecular Oxygen: Syntheses and Crystal and Molecular Structures of the Uranyl Thiolate Peroxo Species (HNEt3)2[(UO2)2(O2)(SC4N2H3)4] and (HNEt3)[H(UO2)2(O2)(SC4N2H2Me)4].cntdot.Me2CO.cntdot.0.5Et3N and of the Uranyl Thiolate Oxo Cluster (HNEt3)2[(UO2)4(O)2(SC5NH4)6].cntdot.Me2CO

Synthesis and Characterization of Binuclear Oxo-Vanadium Complexes of Carbon Oxoanion Ligands. Crystal Structures of the Binuclear Vanadium(IV) Complex (NH4)[V2O2(OH)(C4O4)2(H2O)3]·H2O, of the Mixed-Valence Vanadium(V)/Vanadium(IV)-Squarate Species [(n-C4H9)4N][V2O3(C4O4)2(H2O)3]·3H2O and [(C4H9)4N]4[V4O6(C4O4)5(H2O)4]·6H2O, and of the Binuclear Vanadium(IV)-Oxalate Species [V2O2Cl2(C2O4)(CH3OH)4]·2Ph4Cl

The synthesis and characterizations of the monomeric group III thiolate complexes [In(SC{sub 5}H{sub 4}N){sub 3}](1), [In(SC{sub 5}H{sub 3}N-3-SiMe{sub 3}){sub 3}](2), and [Ga(SC{sub 5}H{sub 4}N){sub 3}] (5) and of the binuclear alkoxy-bridged derivatives [M{sub 2}(OC{sub 2}H{sub 5}){sub 2}(SC{sub 5}H{sub 4}N){sub 4}] (M=In (3), Ga (6)) are described. Compounds 1 and 2 are formed in the reaction of the appropriate nitrate salt M(NO{sub 3}){sub 3}{center_dot}xH{sub 2}O with the pyridine-2-thiol derivative in ethanol or water in the presence of triethylamine. In contrast, when the reaction is carried out under strictly anaerobic conditions, using the appropriate metal chloride MCl{sub 3} in ethanol solution, the binuclear species 3 and 6 are obtained. Compound 5 was prepared using GaCl{sub 3} in THF with pyridine-2-thiol under strictly anaerobic conditions. Compound 4 was prepared under anaerobic conditions in THF solvent from GaCl{sub 3} and pyridine-2-thiol. Attempts to prepare complexes of the 3,6-bis(tertbutyldimethylsilyl)pyridine-2-thiol ligand type were unsuccessful. However, the sodium salt [Na(SC{sub 5}H{sub 2}N-3,6-(SiMe{sub 2}Bu{sup 1}){sub 2})]{sub 6}{center_dot}2(C{sub 2}H{sub 5}){sub 2}O (7) was isolated and the structure characterized.

Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC5H4N)3] (M = Ga, In), [In(SC5H3N-3-SiMe3)3], and [M2(OC2H5)2(SC5H4N)4] (M = Ga, In)

Synthesis, Spectroscopy, and Structural Characterization of Six-Coordinate Bis(aryldiazenido)rhenium and Bis(diarylhydrazido)rhenium Complexes. X-ray Structures of (Et4N)[Re(NNPh)2(O2C6H4)2], (Et4N)[Re(NNPh2)2(O2C6H4)2], and Na[Re(NNPh)2(O2C6H4)2].cntdot.CH3CN

The reaction of PPh4[VO2Cl2] with PhAsO3H2 in acetonitrile for 36 h at 100 °C and autogenous pressure yields [(V2O3)(Ph6As6O14)], an unusual cluster with a {V2O3}4+ core straddled by the hexadentate ligand {Ph6As6O14}4–, which forms via thermally induced condensation of PhAsO3H2 groups.

Yuan Da Chang

Papers

Synthesis and Characterization of Gallium and Indium Thiolate Complexes. Crystal and Molecular Structures of [M(SC5H4N)3] (M = Ga, In), [In(SC5H3N-3-SiMe3)3], and [M2(OC2H5)2(SC5H4N)4] (M = Ga, In)

Synthesis, Spectroscopy, and Structural Characterization of Six-Coordinate Bis(aryldiazenido)rhenium and Bis(diarylhydrazido)rhenium Complexes. X-ray Structures of (Et4N)[Re(NNPh)2(O2C6H4)2], (Et4N)[Re(NNPh2)2(O2C6H4)2], and Na[Re(NNPh)2(O2C6H4)2].cntdot.CH3CN

Investigations of the V/O/RAsO32– system: solvothermal synthesis and crystal and molecular structure of [(V2O3)(Ph6As6O14)]