Kaluo Tang

Formation and X-ray structure of a novel tetradecanuclear silver cluster complex, Agl4(μ6-S)(SPh)12(PPh3)8 · 4CH3OH · 13H2O

Abstract A neutral tetradecanuclear silver thiolate complex has been formed from the reaction of (Ph3P)2Ag(S2CSPh) with CH2Cl2 and McOH, and structurally characterized by X-ray diffraction analysis. The core of the cluster [Ag14(μ6-S)(SPh)12(PPh3)8] contains an Ag14S12 cage composed of staggered Ag6, Ag8 S2 polyhedra. There is μ6-sulfur atom at the centre of the cage, which is weakly bonded to six silver atoms of an Ag6 octahedron. Eight terminal PPh3 ligands are coordinated to the other eight silver atoms, which form an Ag8 cube. Twelve S atoms of a S12 icosahedron bridge the Ag6 and Ag8 polyhedra.

Synthesis and crystal structure of a polymeric complex [S4Cd17(SPh)24(CH3OCS2)4/2]n·nCH3OH

Abstract The three dimensional polymeric complex [S 4 Cd 17 (SPh) 24 (CH 3 OCS 2 ) 4/2 [ n · n CH 3 OH ( 1 ) has been synthesized from the reaction of [Cd 4 (SPh) 6 (SPh) 4/2 [ n with CS 2 , DMF and MeOH, and structurally characterized by X-ray diffraction analysis. Its repeat unit is a 17-nuclear cadmium cluster which is linked to four surrounding aggregates through four CH 3 OSC 2 ligands. The method of synthesis is also discussed.

Insertion of CS2 into Ag–S bonds. Preparations and crystal structures of[{[Ag(SC6H2Pri3-2,4,6)]4·CHCl3}n] and its insertion product with CS2, [{Ag(S2CSC6H2Pri3-2,4,6)}2{Ag(SC6H2Pri3-2,4,6)}6]·8CHCl3

By the use of a sterically hindered arenethiolate ligand, 2,4,6-Pri3C6H2SH the colourless silver thiolate complex [{[Ag(SC6H2Pri3-2,4,6)]4·CHCl3}n](1) has been synthesized and structurally characterized. The structure of (1) consists of a one-dimensional double (Ag–SR)n strand belt polymer. The strand (Ag–SR)n is formed by alternating silver and sulphur atoms of the ligands. Complex (1) reacts with a small amount of CS2 to give a pale yellow product [{Ag(S2CSC6H2Pri3-2,4,6)}2{Ag(SC6H2Pri3-2,4,6)}6]·8CHCl, (2), and CS2 is inserted into a quarter of the Ag–S bonds of complex (1). The unusual structure ofcomplex (2) consists of eight coplanar silver atoms linked through arenethiolate (RS) and aryl thiocarbonate (RSCS2) ligands, exhibiting a number of interesting features. A novel structural type of insertion of CS2 into M–S bonds has been found. Crystal data: (1), triclinic, space group P, a= 14.443(7), b= 16.201 (1 2), c= 16.586(14)A, α= 68.27(6),β= 80.84(6), γ= 75.73(5)°, for Z= 2, R= 0.074, for 2 065 observed reflections; (2), monoclinic, space group P21/n, a= 17.897(7), b= 27.131(18), c= 19.111(9)A, β= 113.59(3)°, for Z= 2, R= 0.084, for 3 930 observed reflections.

STUDIES OF TRINUCLEAR CADMIUM CLUSTER COMPLEXES. SYNTHESES AND CRYSTAL STRUCTURES OF [NMe4][Cd3(SC6H2Pr3 i-2,4,6)7]°C5H12 AND [Cd3(SC6H2Pr3 i-2,4,6)6(HSC6H2Pri 3-2,4,6)]·CH3OH·7H2O

Abstract By the reaction of a sterically hindered arenethiol, 2,4,6-Pri 3C6H2SH, with Cd(NO3)2·4H2O under different conditions, the colourless salt of trinuclear cadmium cluster anion complex [NMe4][Cd3(SC6H2Pri 32,4,6)7]. C5H12 (1) and the uncharged trinuclear cadmium complex [Cd3(SC6H2Pri 32,4,6)6(HSC6H2Pri 32,4,6)]°CH3OH·7H2O (2) have been synthesized. These have in turn been structurally characterized. Crystals of (1) are monoclinic, space group P21 ln with a = 19.629(6), b = 25.608(9), c = 25.450(9)A, β = 107.54(3)°, V- 12203(7)A3, Z = 4, R = 0.076 for 3839 observed reflections. Crystals of (2) are triclinic, space group P 1 with a = 19.792(10), b = 20.508(12), c = 33.97(2)A, α = 85.81(5), β = 86.77(5), γ = 85.12(4)°, V = 13686(14)A3, Z = 4, R = 0.0921 for 8327 observed reflections. The core of the cluster anion of (1) [Cd3(SC6H2Pri 32,4,6)7]− is formed by a defect cubane unit with three cadmium and four sulphur atoms at its vertices. Each cadmium atom exhibits tetrahedral coodrination with one termi...

Synthesis and crystal structure of a novel keggin-type isopolyoxomolybdate [Bu4N]6[H3O]2[Mo13O40]2

Abstract Solid-state reaction of (NH4)6Mo7O24 · 4H2O with Bu4NBr and NH2OH · HCl at low temperature yields an isopolyoxomolybdate [Bu4N]+6[H3O]+2[Mo13O40]4−2, the structure of which has been determined by X-ray crystallography. The title compound contains two [Mo13O40]4− anions which have different symmetry. Both anions have Keggin-type structures with a molybdenum atom centre.

Synthesis and X-ray crystal structure of hexakis(μ-(p-tert-butylthiophenolato))-mono(p-tert-butylthiophenolato) trichloro-tetracadmate(II) dianion

Abstract A tetranuclear chlorine-containing cage thiolate cluster complex of cadmium, [HNEt3]2[Cd4(μ-SC6H4But-4)6(SC6H4But-4)Cl3], consisting of a Cd4(μ-S)6 adamantane-like cage, was synthesized directly from the reaction of a cadmium salt and corresponding thiolate. The chloride ions, introduced unexpectedly, act as terminal ligands.

Synthesis and X-ray crystal structure of [NMe4][Cd3(SC6H2Pri3)7]·C5H12

The core of the cluster anion [Cd3(SC6H2Pri3)7]– is formed by a defective cubane unit with three cadmium and four sulphur atoms at its vertices; each cadmium atom exhibits tetrahedral coordination with one terminal sulphur, two doubly bridging sulphur and one triply bridging sulphur atoms.

Synthesis and Structure of two I(Arylperthiocarboxylato) (Aryldithiocarboxylato) (pyridine)2dicopper(I)] complexes

Abstract The structures of [Cu2(S3CC6H5)(S2CC6H5)py2] (I) and [Cu2(S3C-p 6H4CH3)(S2C-p-C6H1CH3)py2] (II) have been determined by X-ray methods. Crystals of I are monoclinic, space group P21/c, with a = 9.718(4), b = 10.698(4), c = 24.995(9) A, β = 92.77(3)°, Z = 4; crystals of II are triclinic, space group P1, with a = 7.802(6), b = 11.990(7), c = 14.630(7) A, α = 91.76(4), β = 95.76(4), γ = 93.25(5)°, Z = 2. The structures have been solved by diŕect and Fourier methods and refined to R = 0.058 for I and R = 0.090 for II. Both complexes show a dimeric configuration in which the geometries around the two copper atoms are different. The dithio group acts as bridging planar ligand between the two metal atoms; the perthio group acts as a chelate for the first copper atom, while its terminal sulfur atom also bridges the two metal atoms. Two pyridine molecules complete the coordination of the second copper atom to form a distorted tetrahedron.

Syntheses, structures and properties of novel molybdenum and tungsten complexes of fullerenes

The synthesis and characterization of several fullerene-based organometallic complexes containing Mo and W is reported.

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF [Cd2(OS2CSC6H2Bu t 3-2,4,6)4(C2H5OH)2] · C2H5OH. A PRODUCT OF INSERTION OF CARBON DISULFIDE INTO Cd-S BONDS

Abstract The title compound, C82H134Cd2O7S12, formed by reaction of the corresponding cadmium thiolate with CS2 and recrystallization from acetone/ethanol in air. Crystals belong to the triclinic space group P 1, with Z = 2, cell dimensions a = 14.647(13), b = 19.140(20), c = 20.967(10)A, α = 64.79(6), β = 79.56(5), γ = 71.48(7)°, V = 5034A3. The structure was solved by direct methods and was refined to an R of 0.098 for 3754 observed reflections. All the Cd-S bonds were inserted by CS2, then the ligands were oxidized to form unusual ArSCS2O− groups. Cadmium atoms have distorted octahedral geometry. The distance between the two Cd atoms is 3.753A.