Xianglin Jin

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.

A novel synthetic route to titanoxacycle complexes

Abstract In the presence of lithium bromide, reactions of lithium {3-(o-methoxyphenyl)pentyl}cyclopentadienide with CpTiCl3, MCl4 (M = Ti, Zr) led to a novel formation of M O bondsvia multiple bond cleavage of Me O and M Cl bonds.

The synthesis, crystal structure and synergistic fluorescence effect of a heteronuclear lanthanide complex (HLC) {Na3TbLa2(C7H3SO6)4·26H2O}n

Abstract Sodium sulpho-salicylate (C7H4SO6Na2) reacts with terbium perchlorate to form Tb(OH)(C7H3SO6)H2O (A) which reacts with lanthanum perchlorate to give the title complex Na3TbLa2(C7H3SO6)4·26H2O (B) whose cyrstal structure was determined. The TbIII and LaIII ions are bridged by tridentate and tetradentate carboxylic groups. The complex is a polymeric molecule formed by a repeating trinuclear HLC structural unit. TbIII is eight-coordinated dodecahedral and LaIII is 10-coordinated with a distorted bicapped square antiprismatic configuration. The excitation and emission spectra showed that the maximum excitation wavelength of A is 356 nm, which is 12 nm greater than that of B, 344 nm. Both A and B have the same emission spectra at their excitation wavelengths 356 and 344 nm; the fluorescence intensity of B is 3.3 times that of A at the maximum emission wavelength 543 nm. The fluorescence enhancement of non-fluorescent ions (NFI) such as LaIII for the fluorescent ions (FI) such as TbIII in one molecule is known as “synergistic fluorescence effect”, which is different from co-fluorescence resulting from the mixing of NFI complex with FI complex. The relationship between the structure and properties is discussed.

SYNTHESIS OF ONE-AND TWO-DIMENSIONAL ZINC AND CADMIUM COMPLEXES WITH 4, 4′-BIPY

Abstract The zinc(II) and cadmium(II) complexes [Zn(4, 4′-bipy)(SCN)2]∞ 1 and [Cd(4, 4′-bipy)-(SCN)2]n 2 have been synthesized and their crystal structures determined by X-ray crystallography. Complex 1 is monoclinic, space group C2/c, with a = 18.076(5), b = 5.190(1), c = 17.315(4)A; β = 115.54(2), V = 1465.8(8)A3, calculated density 1.530gcm−3, Z = 4. In this compound, the rod-like ligand 4, 4′-bipy bridges Zn(II) centres, and the NCS groups are terminally coordinated. (N-Zn-N) is 108.5°, resulting in the formation of a zigzag Zn-bipy-Zn chain. These chains are arranged in parallel fashion. The 4, 4′-bipy ligands of adjacent layers are separated by 3.95 (A). Complex 2 is monoclinic, space group C2/c, a = 11.902(2), b = 11.745(2), c = 10.500(2)A; β = 109.71(3), V = 1381.8(4)A3 calculated density 1.849gcm−3, Z = 4. In this structure, the cadmium(II) ion is slightly distorted octahedral and the SCN groups act as doubly bridging ligands connecting cadmium atoms to form zigzag chains, separated by 4, 4′-bipy...

A tetranuclear copper(I) cluster complex with a benzeneselenolate ligand, (Me4N)2[Cu4(SePh)6].CH3OH

The structure of bis(tetramethylammonium) hexakis-(μ-benzeneselenolato)tetracuprate(I) methanol solvate, (C 4 H 12 N) 2 [Cu 4 (C 6 H 5 Se) 6 ].CH 3 OH, is composed of a Cu 4 Se 6 adamantane-type cluster anion and a bulky cation. The cluster anion, [Cu 4 (SePh) 6 ] 2- , can be considered as a tetrahedron of Cu atoms inscribed in a distorted octahedron of Se atoms. The Cu atoms are in a distorted trigonal-planar coordination, which includes three μ 2 -Se atoms.

A SYNTHESIS AND STRUCTURE OF A WATER-SOLUBLE TETRAPYRIDYLPORPHYRINATO TIN(IV) CHLORIDE

Abstract The water-soluble octahedral tin(IV) porphyrin complex, SnCl2tpyp, was synthesized via reaction of H2tpyp with anhydrous SnCl2. The crystal structure of this complex has been determined at room temperature. The tin(IV) atom is coordinated by four nitrogen atoms in a square-planar fashion with an average Sn-Np bond distance of 2.081(9)A, and the coordination sphere is completed by two axial chloro ligands with an average Sn-Cl bond distance of 2.435(5)A, Cl-Sn-Cl = 180.0 (1)°. Crystal data: a = 12.385(12), b = 26.88(2), c = 14.882(9)A, β = 94.16 (7)°, monoclinic, space group C2/c, V = 4941A3, Z = 4, C46H48Cl2N8O6Sn, 2687 observed data, R = 0.085.

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.