Wang Ru-Ji

Synthesis and X-ray crystal structure of μ-terephthalato nickel(II) binuclear complex [Ni2(TPHA)(bpy)4](ClO4)2

Abstract The X-ray crystal structure of the complex [Ni2(TPHA)(bpy)4](ClO4)2 (TPHA = terephthalato, bpy = 2,2′-bipyridine) has been determined. Its structure consists of a terephthalato bridged nickel(II) binuclear cation and non-coordinated perchlorate anions. In the complex the TPHA bridges are in a bis bidentate configuration. The environment of the nickel(II) ion is distorted octahedral.

The study of isolobal displacement reactions. Synthesis and structures of the heterobimetallic μ-alkyne cluster complexes η-RC5H4(CO)2M(μ-R1C2R2)Co(CO)3 (MMo, W; RCH3C(O), CH3O2C)

η-CH3C(O)C5H4(CO)2Mo(μ-C6H5C2C6H5)Co(CO)3 (1a),η5-CH3C(O)C5H4(CO)2Mo(μ-p-CH3C6H4C2C6H5)Co(CO)3 (1b), η5-CH3O2CC5H4(CO)2Mo(μ-C6H5C2C6H5)Co(CO)3 (1c), η5-CH3C(O)C5H4(CO)2W(μ-C6H5C2C6H5)Co(CO)3 (1d) and η5-CH3O2CC5H4(CO)2W(μ-C6H5C2C6H5)Co(CO)3 (1e) were prepared by reactions of the corresponding sodium salts of functionally substituted cyclopentadienyl carbonyl molybdenum (tungsten) anions with (CO)3Co(μ-C6H5C2C6H5)Co(CO)3 or (CO)3Co(μ-p-CH3C6H5C2C6H5)Co(CO)3, respectively. The compounds 1a-1e were characterized by elemental analysis, IR, 1H NMR and mass spectroscopy, while the structure of 1c was further established by X-ray diffraction analysis. The compound crystallizes in the monoclinic space group P21/n with a = 8.503(1), b = 26.721(7), c = 11.033(2) A; β = 106.09(2)°; V = 2408 A3; and Z = 4.

Pentakis(triphenylphosphine oxide)chlorolanthanide bis(feric tetrachloride) complexes

Abstract Twelve new complexes with the general formula [(Ph 3 P=O) 5 LnCl][FeCI 4 ] 2 where Ln=La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er and Y were synthesized. The X-ray diffraction crystal structural analysis of [(Ph 3 P=O) 5 LaCl] [FeCl 4 ] 2 showed that the [(Ph 3 P=O) 5 LaCl] 2+ cation was of six coordinated distorted octahedral geometry and the [FeCl 4 ] − anion was of tetrahedral geometry. The INDO method study revealed that the coordination of PO groups to the lanthanide made the LnCl bond more reactive than that in LnCl 3 , so that Lewis acids, such as FeCl 3 , could abstract chloride to give the title complexes.

Formation and structure of [Co{Ph2PN(iBu)PPh2-P,P′}2(CO)][Co)(CO)4] - a cage molecule-pair or an ion-pair complex?

The strong π-acid ligand Ph2PN(iBu)PPh2 reacts with Co2(CO)S (1:1) to give Co2[μ-Ph2PN(iBu)PPh2] (μ-CO)2(CO)4 (1); however, when the ratio is 2:1 a novel species [Co{Ph2PN(iBu)PPh2-P,P′}2(CO)][Co(CO)4] (2) has been obtained. Crystal data for 2: Mr = 1140.83; triclinic, space group P1, a = 12.330(2), b = 13.340(2), c = 18.122(3) A, α = 86.63(1), β = 80.75(1), γ = 84.24(1)°, V = 2924 A3, Z = 2; R = 0.060 for 3711 reflections having I ⩾ 3σ(I). The results of X-ray diffraction, ESR, variable-temperature magnetic susceptibility, conductivity, and XPS analysis support that the species 2 is a d9-d9 cage molecule-pair. The mechanism for the formation of the species 2 has been investigated initially by 31P NMR.

Crystal structure of the complex of dibenzo-30-crown-10 with dysprosium isothiocyanate

Crystalline [Dy(NCS)3(dibenzo-30-crown-10)(H2O)2]·H2O·MeCN can be obtained by slowly evaporating a reaction mixture of Dy(NCS)3·nH2O with dibenzo-30-crown-10 in a solution of acetonitrile. The material crystallizes in the monoclinic space groupP21/n, the cell parameters area=11.450(5),b=23.284(4),c=18.424(6)Å, β=106.28(4)°,V=4715Å3,M=968.47,Dx=1.36 g cm−1, μ=17.80 cm−1,F(000)=1972,Z=4.2740 independently observed [I≥3σI] reflections were used in the final least-squares refinement leading to an agreement index ofR=0.085. The Dy(III) ion coordination geometry approximates a square antiprism, involving two water oxygens and three dibenzo-30-crown-10 oxygen atoms and three isthiocyanate nitrogens. Hydrogen bonds are formed between the two water molecules and four uncoordinated crown ether oxygen atoms.

SYNTHESIS AND MOLECULAR STRUCTURE OF NOVEL BINUCLEAR COBALT COMPLEX WITH MIXED VALENCE STATE Co(I)Co(II) (μ-Ph 2 Ppy) 2 (μ-CO) 2 Cl 3

A novel binuclear cobalt complex with mixed valence state Co(Ⅰ)Co(Ⅱ)(μ-Ph_2Ppy)_2(μ-CO)_2Cl_3 has been prepared, Ph_2Ppy=2-(diphenyl phosphino)pyridine, and its molecular structure determined by using 3569 independent reflections. The complex was crystallized in the orthorhomblc space group P2_1nb with a=13.32(1), b=14.31(1),c=18.94(2) and Z=4. The structure was solved by direct method and full-matrix least squares refinement carried out. The final R value is 0.072.If the Co-Co bond is not taken into account, two cobalt atoms exhibit a five-coordlnate reformed trigonal bipyramid configuration (formal oxidation state +1) and a six-coordinate reformed octahedral configuration (formal oxidation state +2), respectively. The Co-Co distance is 2.685(1). The molecule belongs to the C_(2v), point group. A new W-frame compound with mixed valence state Co(0)Co(Ⅰ)(μ-Ph_2Ppy)_2(μ-CO)(CO)Cl can be formed by reducing this complex.