Qiang-Jin Wu

The synthesis and crystal structure of a novel cubane-like molybdenum copper sulfur cluster [Mo3CuS4]·[S2P(OC2H5)2]3·I·CH3COO·HCON(CH3)2

Abstract The synthesis and crystal structure of a novel cubane-like cluster with a [Mo3CuS4] cluster core is reported herein. This compound was prepared from CuI upon reaction with the trinuclear molybdenum cluster {Mo3S4[S2P(OC2H5)2]4}·H20. The title compound crystallizes in a triclinic space group P 1 with the following unit cell dimensions: a= 12.639(3); b=13.722(2); c=14.644(2); α= 108.78(1); β=106.36(1); γ=102.54(1)°; Z=2; V=2124 ,A3; Dc=2.022 g cm−3. 7491 independent reflections were collected on a CAD-4 four-circle diffractometer with Mo Kα radiation in the range 1°

Synthesis, structure and electrochemical behaviour of cobalt(II) complexes with 2,6-bis(benzimidazol-2′-yl) pyridine

SummaryThe complexes Co(BBP)Cl2, Co(BBP)2SO4·H2O, Co(BBP)2(NO3)2·H2O, Co(BBP)2(ClO4)2 and Co(BBP−H)2· 2H2O, where BBP is 2,6-bis(benzimidazol-2′-yl) pyridine, were prepared and characterized by elemental analysis, electrical conductance, i.r. and electronic spectra. The electrochemical behaviour of the complexes was recorded and the X-ray crystal structure of Co(BBP)Cl2(MeOH)2 was determined. The geometry about cobalt is a distorted octahedron.

Preparation and characterization of a novel asymmetrically oxidized complex of 2-(diphenylphosphino)-benzenethiol with ruthenium. The crystal and molecular structure of [Ru(2-Ph2PC6H4S)·(2-Ph2PC6H4S−OH)(2-Ph2PC6H4SO2)]·1/2H2O

SummaryThe reaction between [RuCl2(PPh3)3] and 2-(diphenylphosphino)-benzenethiolate anion (DPPBT) yields the 18-electron RuII complex [Ru(DPPBT)3][HNEt3] (1), which is readily oxidised first to the neutral RuIII complex [Ru(DPPBT)3] (2), and then to the 18 electron RuIII complex [Ru(2-Ph2PC6H4S)(2-Ph2PC6H4S−OH)·(2-Ph2PC6H4SO2)]·1/2H2O (3). The x-ray crystal structure of complex (3) reveals it has a pseudo-octahedral geometry.One sulphur has been oxidised to a sulphinic acid (S−OH) group and a second to a sulphinate (SO2) group, both being ligatedvia sulphur.

Synthesis and crystal structure of a new μ2-phenoxy oxygen bridged macrocyclic binuclear cadmium(II) complex with pendant arms

Abstract A new binuclear cadmium(II) macrocyclic complex has been synthesized by [2 + 2] Schiff-base condensation of tris(3-aminopropyl)amine with sodium 2,6-diformyl-4-methoxylphenolate in the presence of Cd(ClO 4 ) 2 · 6H 2 O. The crystal structure, spectral characterization and molar conductivity show that two cadmium(II) ions were bridged by two μ 2 -phenoxy oxygen atoms. Each cadmium(II) is located in a trigonal prismatic coordination environment (N 4 O 2 ).

Synthesis, structure and magnetic properties of oxo-centered trinuclear manganese complex [Mn3O(O2CC3H7)6(C5H5N)3]·ClO4

Abstract The reaction of N-n-Bu4MnO4 with Mn(OAc)2·4H2O, pyridine and butyric acid in absolute EtOH leads to the high-yield formation of the oxo-centered trinuclear Mn complex, [Mn3O(O2CC3H7)6(C5H5N)3]·ClO4. The complex crystallizes in orthorhombic, space group Pna21 with a=19.588(7), b=20.194(6), c=12.491(5) A. Variable temperature solid state magnetic susceptibility study shows that the antiferromagnetic exchange interaction is weak, and the exchange integral J=−12.36 cm−1.

The synthesis and crystal structures of the first species of monocubane type clusters [Mo3PbS4]6+ and [Mo3BiS4]7+

The synthesis and crystal structure of two heteronuclear transition metal-main group metal cubane-like cluster compounds [Mo 3 (PbI 3 )S 4 (dtp) 3 (py) 3 ] ( I ) and [Mo 3 (BiI 3 )S 4 (μ-OAc)(dtp) 3 ·(py)]·(CH 3 ) 2 CO( II ) (dtp=S 2 P(OC 2 H 5 ) 2 − ;OAc=(OOCCH 3 ) − ) are reported. They resulted from the reaction of trinuclear Mo 3 S 4 (dtp) 4 ·H 2 O with PbI 3 − and BiI 3 , respectively. Both of the molecular structures have an [Mo 3 MS 4 ] core (Mue5f8Pb, Bi) but their molecular configurations are different. The electron transfer of a lone pair electrons of M metals occurs in the additive clusters I and II , thus enhancing the Moue5f8Mo bonding. Evidence for this is seen in the 95 Mo NMR spectrum before and after the addition reaction. Crystal data: I : triclinic, P l, a = 11.087(2), b = 12.760(5), c = 19.358(4), A, α = 94.37(3), β = 92.39(2), γ = 99.46(2)°, V = 2689(2), A 3 , Z = 2. Least-squares refinement of 4462 reflections gave a final agreement factor of R = 0.052 ( Rw = 0.058); II : triclinic, P l, a = 11.696(4), b = 13.044(4), c = 18.241(6), A, α = 74.90(3), β = 75.96(3), γ = 88.06(3)°, V = 2605(3)A 3 , Z = 2. Least-squares refinement of 5913 reflectioins gave a final agreement factor of R = 0.054 ( Rw = 0.061).

Ligand-cluster reactivity and structure relationship; the synthesis, structural characterization and properties of two new MoCuS cluster compounds

By using Mo3S4(dtp)4·H2O (dtp = S2P(OEt)2) as starting material and from the substitution reaction of ligands and the addition reaction with CuI, two novel Moue5f8Cuue5f8S cubane-like cluster compounds {[CuMo3S4]·I·(μ-dtc)(dtc)3·py}· CH3COOC2H5 (5) and {[CuMo3S3X·I·(O)2(dtcpyr)3dpy}(CH3COOC2H5)0.6(H2O)0.4 (6) (X34O+ 14S, dtc + S2CN(Et)2, dtcpyr = S2CN(C4H8)) have been obtained. The synthesis, structural characterization and properties of these two clusters as well as their comparison with dtp structural analogues are described. The ligand—cluster reactivity and structure relationship is also discussed. Crystal data: for 5 space group P1 a = 16.22358(6), b = 16.220(9), c = 11.421(5) →A, α = 104.004(4), β = 110.54(4), ψ = 87.23(5)°, Z = 2,4809 reflections, R = 0.041; for 6; space group P21/n, a = 15.179(9), b = 16.353(6), c = 17.621(9) A, β = 112.18(5)°, Z = 4, 3469 reflections, R = 0.047.

A monomeric ruthenium thiolato complex with a chelated η6-arene ligand. The preparation and structure of [Ru{2-η6-Ph)-6-PhC6H3S}- (2,6-Ph2C6H3S)(PPh3)]

Abstract Reaction of [RuCl 2 (PPh 3 ) 3 ] with the 2,6-diphenylthiophenolate anion (DPT) gives the complex [Ru(η 6 - DPT)(DPT)(PPh 3 )], with one thiol phenyl substituent η 6 -bonded to the ruthenium. The X-ray crystal structure reveals a distorted piano stool type of geometry. Crystal data: space group P 2 1 / c , a =14.204(4), b =9.503(5), c =31.680(9) A, β=97.40(3)°, Z =4. The η 6 -arene ligand is labile and can readily be replaced by CO and 1,2- bis(diphenylphosphino)ethane.

The synthesis and crystal structure of a novel dinuclear molybdenum compound with a single sulfur bridge [(CH3)4N]2[Mo202S(S2)4]·CH3CN

Abstract A novel dinuclear molybdenum compound with a single sulfur bridge is reported herein. It is the first example of a dinuclear molybdenum compound containing a [Mo202S] structural complex. The title compound crystallizes in a monoclinic space group P21/n with the following unit cell dimensions: a= 9.281(2), b=14.712(6), c=18.699(7) A, β= 95.10(3)°, V=2543 A3, Z=4,Dc=1.833 g cm−3. Diffraction data of 3810 reflections with I⩾ 3σ(I) have been collected on a CAD-4 four-circle diffractometer using Mo Kα radiation. The structure has been determined by Patterson and direct methods and refined by a least-squares method to a final R index of 0.053. The structure determination shows that the angle between the molybdenum atoms Moue5f8Sue5f8Mo is 91.59(4)°.

The synthesis and crystal structure of novel Mo-Sn tetranuclear cubane-like cluster [Mo3(SnBr3)(μ3-O)(μ3-S)3(dtp)3(py)3]·(CH2Cl2)

The synthesis and crystal structure of the first example for hybrid Sn-Mo tetranuclear cubane-like cluster compound containing S/O mixed triple capping atom [Mo3(SnBr3)(μ3-O)(μ3-S)3(dtp)3(py)3]·(CH2Cl2) (A) (dtp=S2P(OC2H5)2) are reported. The compound is prepared by the reaction of [Mo3(μ3-O)(μ-S)3(dtp)4·(H2O)] with SnBr3−. The molecular structure of the cluster can be described as a [Mo3OS3] core with the SnBr3− fragment linked to {Mo3} triangle by three (μ3-S). Three Mo-Mo bond lengths are 2.616(2), 2.620(2), 2.628(2) Å, respectively, and the molecule has approximately C3v symmetry. There is no bonding between Sn and Mo atoms, however, the addition of SnBr3− may cause electron transfer from Sn2+ to [Mo3OS3] core to result in the shortening of Mo-Mo bond distances. The compound crystallizes in the monoclinic space group P21/n with refined lattice parameters ofa=13.012(4),b=22.877(6),c=18.585(6) Å,β=96.34(3)°,V=5498(3)Å3, andZ=4. Full matrix refinement converged with final agreement factor ofR=0.054,Rw=0.064.