Hong Maochun

Heteronuclear W(Mo)CuS complexes of dialkyldithiocarbamate. Syntheses of (Et4N)2[MCu3S4(dtcR2)3] and structures of (Et4N)2[MCu3S4(dtcC5H10)3]· DMF (M = W or Mo)

Compounds (Et 4 N) 2 [MCu 3 S 4 (dtcR 2 ) 3 ] (M=W ( 1 ) or Mo ( 2 ); R 2  C 5 H 10 ( a ), Et 2 ( b ) or C 4 H 8 ( c ) were synthesized by the reaction of (Et 4 N) 2 MS 4 and CuCl in the presence of NadtcR 2 in DMF . The crystal and molecular structures of 1a·DMF and 2a·DMF were determined from X-ray diffraction data. The compounds are isomorphous and crystallize in the triclinic space group P with unit cell parameters for 1a(2a)·DMF : a =12.047(0) (12.053(2)), b = 17.620(3) (17.650(5)), c =14.514(1) (14.533(4)) A; α=100.83(9) (100.43(3)), β=115.41(3) (115.47(2)), γ=79.49(8) (79.78(2))°; V =2715.9 (2727.8) A 3 , Z =2 (2), and D x =1.611 (1.497) g/cm 3 . The final R values converged to 0.048 and 0.067 for M=W and Mo respectively. [p ]The four metal atoms MCu 3 are coplanar with the central tetrahedron of MS 4 preserved. Each Cu(I) ion is coordinated to two inorganic S atoms from MS 4 and two organic S atoms from one dtcC 5 H 10 ligand in a distorted tetrahedral geometry. Infrared spectra showed two stretching vibrations at 430–442 cm − for μ 3 -SM and 455–463 cm −1 for μ 2 -SM. The compounds are diamagnetic and show reversible one-electron oxidation-reduction at E 1/2 = 0.55 V (2a) .

A novel tungsten-copper-sulfur cluster with dialkyldithiocarbamate: preparation and structure of (Et4N)2 [W2Cu5S8(S2CNMe2)3]

We report the synthesis and structure of a novel cluster compound (Et 4 N) 2 [W 2 Cu 5 S 8 (S 2 CNMe 2 ) 3 ] consisting of two defective cubane cores, WCu 2 S 4 and WCu 3 S 4 , bridged by two Me 2 dtc − ligands and jointed by two weak Cu-S bonds

Reaction of sulfur-containing structural units of transition metals

Two tri-n-butylphosphine-participated (PBu 3 n ) nickel (II) complexes of 2-mercaptophenol (H2mp), i.e. Ni2Ru(mp)3(Hmp)(PBu 3 n )3 3 exhibiting a curved heterotrinuclear metal skeleton and its mononuclear “synthon”, [HNEt3 ] [ Ni(mp) (Hmp) (PBu 3 n )] 1 were synthesized and characterized by X-crystallography and1H NMR, FAB-MS and cyclic valtammogram measurements. The nickel (II) center in 1 has a square-planar geometry. For 3, the ruthenium (III) atom is in a distorted octahedral environment and the two nickel (II) atoms exhibit squareplanar and rare triangle-planar geometries, respectively. The Ni (1) -Ru-Ni(2) arrangement is severely asymmetric with the distances 0.254 and0.394 nm, respectively, for Ni(1)-Ru and Ni(2)-Ru. The structural regularities of relevant complexes are summarized in relation to the structural as well as spectra data.