Xiao-Ying Huang

A novel bonding mode of tetrazolate ligand to a metal: synthesis and structural characterization of 5-phenyltetrazolate organolanthanide complexes: [{(C5H4Me)(C5H5)LnTz}2][{(C5H4Me)2LnTz}2] (Ln=Dy, Gd) and [(C5H4Me)2LnTz)]2 (Ln=Yb, Er)

Reaction of (C 5 H 4 Me) 3 Ln and TzH (5-phenyl-1H-tetrazole) in THF affords complexes [(C 5 H 4 Me) 2 LnTz] 2 [Ln=Yb ( 1 ), Er ( 2 )]. 1 crystallized in the space group C 2/ c , with unit cell dimensions a =25.596(2), b =8.342(1), c =21.573(2) A, β =129.322(9)°. V =3563.5(8) A 3 and Z =8 for D c =1.776 g cm −3 . Least-squares refinement of the model based on 2700 reflections converged to a final R =0.031. The molecule is centrosymmetric dimer in which each ytterbium atom is coordinated by two methylcyclopentadienyl groups and three nitrogen atoms of the bridging Tz ligands to form a distorted trigonal-bipyramidal geometry. When there is a small amount of (C 5 H 4 Me) 2 Ln(C 5 H 5 ) in (C 5 H 4 Me) 3 Ln, the 1:1 complexes [{(C 5 H 4 Me)(C 5 H 5 )LnTz} 2 ][{(C 5 H 4 Me) 2 LnTz} 2 ] (Ln=Dy ( 3 ), Gd ( 4 )) were obtained in crystalline form. 3 and 4 crystallize as isomorphous crystals of space group P 1 with the following unit cell parameters ( 3 / 4 ): a =9.374(2)/9.420(4), b =13.048(2)/13.215(4), c =16.542(4)/16.677(5) A, a =86.95(2)/87.24(2), β =74.61(1)/74.50(3), γ =77.31(1)/77.08(3)°, Y =1903(1)/1950(1) A 3 , Z =2, D c =1.602/1.545 g cm −3 , R =0.046/0.051. Crystallographic data for 3 and 4 show that there are two disconnected structural units [(C 5 H 4 Me)(C 5 H 5 )Ln( μ - η 1 : η 2 -Tz)] 2 and [(C 5 H 4 Me) 2 Ln( μ - η 1 : η 2 -Tz)] 2 , crystallizing in one asymmetrical unit, each of which is tetrazolate-bridged dimer and has an inversion center. The bridging unit Ln 2 N 6 is planar. All three structures reveal an unusual bonding mode of the tetrazolate ligand, in which the tetrazolate group acts as both a bridging and chelating ligand, with the nitrogen atoms at 1, 2 and 3-position taking part in bonding.

The reaction of (μ3-CCO2R)Co2M(CO)8L (M = Co, Mo, W; L = CO, MeCp; R = Me, Et) with Na2[Fe(CO)4]. X-ray crystal structure analysis of (EtO2CCCCO2Et)Co4(CO)10 and (MeO2CCCCO2Me)FeCo2(CO)9

Abstract The reactions of clusters [(μ 3 - CCO 2 Et ) Co 2 M ( CO ) 8 ( MeCp )][ M = Mo ( 2 a ), W ( 2 b )] , derived from the reactions of (μ3-CCO2Et)Co3(CO)9 with Na[M(CO)3(MeCp)], with Na2[Fe(CO)4] in THF at reflux not only gave the expected metal fragment exchange products [(μ 3 - CCO 2 Et ) FeCoM(CO) 8 ( MeCp ) H ][ M = Mo ( 3 a ), W ( 3 b )] , but also gave the unexpected compounds [(μ 3 - CCO ) FeCoM(CO) 8 ( MeCp )][ M = Mo ( 4 a ), W ( 4 b ) . It is suggested that the formation of two kinds of compounds resulted from two competitive reactions of the intermediates [(μ3-CCO2Et)FeCoM(CO)8(MeCp)]− with acidic treatment: the one is the protonic reaction of the intermediate giving the clusters 3a and 3b; the other is the intermolecular nucleophilic substitution reaction of the intermediate by the catalysis of H+, giving the clusters 4a and 4b. Under the different reaction temperature and molar ratio of the starting materials, the reactions of (μ 3 - CCO 2 R ) Co 3 ( CO ) 9 [ R = Me ( 1 1 ), Et ( 1 b )] [ R = Me ( 6 a ) , Et (6b)] abd (RO2CCCCO2R)FeCo2(CO)9[R = Me (7a), Et (7b)] besides the expected exchange products (μ 3 - CCO 2 R ) FeCo 2 ( CO ) 9 H [ R = Me ( 5 a ), Et ( 5 b )] . This is the first example that the reaction of 6a and 6b with Na2[Fe(CO)4] could produce the clusters 7a and 7b. The clusters (EtO2CCCCO2Et)Co4(CO)10 and (RO2CCCCO2R)FeCo2(CO)9 were determined structurally by X-ray diffraction.

Syntheses, spectroscopy and crystal structure of several binuclear silver(I) cryptates

Abstract Three binuclear silver(I) cryptates were synthesized by template condensation of tris(3-aminopropyl)amine with 5-R-2- methoxy-l,3-phenylenedialdehyde (R=CH3O, CH3 or Br) and characterized by physical measurements (solution electrical conductivity, 1H NMR, IR and electronic spectra). The crystal structure of the cryptate of L1 (R=CH3O) was determined by X-ray diffraction and presents a novel basket structure for the cation [Ag2L1]2+ in which both silver(I) centres possess three coordinate environments. The crystal is monoclinic, space group Cc, C48H68Cl2N8O15Ag2, Mr=1283.75, a=11.349(2), b=29.16(1), c=17.506(6) A, β=102.38(2)°, Z=4, R=0.063 and Rw=0.071 for 3693 reflections. Each Ag atom locates at the top of a trigonal pyramid distorted from a planar triangle composed of one bridgehead tertiary nitrogen and two imino nitrogens. Only two bridging chains of the cryptand coordinate to the metals, another does not. The internuclear distance Ag(1)···Ag(2) is 7.468(12) A. All cryptates possess similar spectroscopic features.

Chiral phosphine ligands derived from sugars 10. Syntheses, structure, characterization, and antitumor activity of the gold(I) complexes with sugar-substructure phosphine ligands

Abstract Gold(I) complexes with sugar-substructure phosphine ligands [Au(n-MBPA)l][n-MBPA = methyl 4,6-O-benzylidene-n-deoxy-n-(diphenylphosphino)-α- d -altropyranoside, HL = I H-pyrimidine-2-thione (2-pymSH), 3,5-dimethyl-1 H-pyrimidine-2-thione (2-pymmSH). 1, n = 2, L = 2-pymS; 2, n = 3, L = 2-pymS; 3, n = 2, L = 2-pymmS; 4, n = 3, L = 2-pymmS]have been prepared and characterized by 1H, 13C and 31P NMR and molecular vibration spectra. Compound 2 crystallizes in the orthorhombic space group P212121, with a = 9.917(4), b = 14.418(6), c = 20.048(7) A, and Z = 4, R = 0.031 for 2493 reflections with I ≥ 3σ(I). The mononuclear compound features a linear geometry for the gold atom defined by important parameters: Au-P 2.256(3) A, Au-S 2.306(3) A and P-Au-S 178.5(1)°. The altropyranose ring in 2 exhibits a distorted chair conformation. The preliminary experiment reveals that the gold(I) complexes with sugar-substructure phosphine ligands possess antitumor activity against P388 leukemia.

Synthesis and structure of a new organolanthanide oxide complex, (CH3C5H4)3Yb4(μ-Cl)6(μ3-Cl)(μ4-O)(THF)3

Reaction of NaCp′ (Cp′ = C5H4CH3) with YbCl3 and YbOCl in THF results in the formation of a new complex, Cp′3Yb4(μ-Cl)6(μ3-Cl)(μ4-O)(THF)3 (1). The X-ray crystal structure of 1 reveals an oxygen-centered tetrahedral arrangement of ytterbium atoms which has μ-Cl groups bridging each edge and a μ3-Cl ligand over the trianglar face composed of Yb atoms with Cp′ groups.

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).

SYNTHESIS AND X-RAY CRYSTAL STRUCTURE OF A MACROCYCLIC BINUCLEAR CADMIUM(II)COMPLEX WITH SIDE CHAIN

Abstract The binuclear cadmium(II) macrocyclic complex was synthesized by [2+2] Schiff base condensation of tris(3-aminopropyl)amine (trpn) with sodium 2,6-diformyl-4-methylphenolate (sdmp) in the presence of Cd 2+ . The crystal structure of the complex [Cd 2 L](ClO 4 ) 2 ·H 2 O·0.5CH 3 OH has been determined by X-ray diffraction. The crystal is orthorhombic, space group Aba 2, a =16.163(6), b =17.714(6), c =16.027(6) A, Z =4, V =4589(5) A 3 , F (000)=2220, R =0.048, R w =0.060. Each cadmium locates at the center of a distorted octahedron composed of three oxygens in the phenoxy groups and three nitrogens in trpn. The coordination of the phenoxy oxygens and terminal amino groups enchanced the stability of the complex.

COPPER COMPLEXES DERIVED FROM 1-(2-CARBOXYBENZOYL)THIOSEMICARBAZIDE (H3L) : SYNTHESES, CHARACTERIZATION AND CRYSTAL STRUCTURE OF CU3L2(PY)6(HIM)(H2O)2

Abstract The reaction of CuCl2·2H2O with 1-(2-carboxybenzoyl)thiosemicarbazide (H3L) and imidazole (HIm) in NaOH gave a CuII complex, which was crystallized from pyridine (Py) to give complex 1, [Cu3L2(Py)6(HIm)](H2O)2. The complex molecule contains a linear Cu3 array in which the central copper atom at the crystallographic inversion centre has an octahedral environment and the other two Cu atoms are square pyramidal, each bridged to the central Cu atom via the L group, with the atoms O(1) and N(2) chelating to Cu(1), and the atoms N(1), S and O(2) to Cu(2). The carboxylate groups coordinate to the metal atoms in a unidentate fashion. Complex 2, [Cu2(H3L)2Cl2](H2O)3, obtained by the reaction of CuCl2·2H2O with H3L has been characterized by IR, UV, NMR (1H and 13C) spectra, and TGA and molar conductance measurements. The ESR and magnetic moment measurements show that the Cu atoms in complex 2 are in the Cu1 oxidation state.

Insertion of dimethylsilanone into a Ln-N bond and X-ray crystal structure of the insertion product [MeCpDy(η2-PzMe2)(μ-η1:η2-OSiMe2PzMe2)]

Abstract Reaction of MeCp 3 Ln(MeCp = COLLABCH 3 C 5 H 4 , Ln = Nd, Gd, Dy) with two equivalents of HPzMe 2 (HPzMe 2 = 3,5-dimethylpyrazole) in THF at room temperature yielded complexes [MeCpLn(PzMe 2 ) 2 ] [Ln-Nd( 1 ), Gd( 2 ), Dy( 3 )], which have been characterized by elemental analysis, IR and MS spectra. The new complexes react with dimethylsilicone grease to give the dimethylsilanone insertion products: [MeCpLn( η 2 -PzMe 2 )( μ-η 1 : η 2 -OSiMe 2 PzMe 2 )] 2 [Nd( 4 ), Gd( 5 ), Dy( 6 )]. The complex 6 has been structurally characterized by X-ray crystallography. 6 crystallizes in the space group P 2 1 / n with unit cell dimensions a =12.066(5), b =11.601(2), c =15.307(3) A, β = 105.84(3)°, V = 2061(1) A 3 , and Z =2 for D Caled =1.63 g cm −3 . Least-squares refinement on the basis of 2930 observed reflections were allowed to reach a final R value of 0.031. The molecule is centrosymmetric dimer in which each dysprosium is coordinated by one methylcyclopentadienyl group, two bridging oxygens, two nitrogens of the chelating PzMe 2 ligand and one nitrogen atom of the bridging PzMe 2 ligand to form a distorted octahedron. The Dy-N(bridging) and Si-N bond lengths are 2.454(5) and 1.803(5) A, respectively. The average Dy-C(ring), Dy-0 and Dy-N(chelating) distances are 2.684(16), 2.294(10), and 2.344(25) A, respectively.

Synthesis and characterization of biscyclopentadienyllanthanide benzothiazole-2-thiolates. X-ray crystal structures of Cp2Ln(SBT)(THF) (Ln=Yb, Dy)

Abstract Cp3Ln (Cp=C5H5, Ln=Yb, Dy, Sm, Y) reacts with an equimolar amount of 2-mercapto-benzothiazole (HSBT) in THF at room temperature to give Cp2Ln(SBT)(THF) [Ln=Yb(1), Dy(2), Sm(3), Y(4)]. All these complexes have been characterized by elemental analysis, IR and MS spectra, indicating they are solvated monomeric structures. The crystal structural analysis shows that in complexes 1 and 2 each lanthanide ion is coordinated by two 5-cyclopentadienyl groups, one oxygen atom of THF, one sulfur and one nitrogen atoms from the chelating benzothiazole-2-thiolate ligand to form a distorted trigonal–bipyramidal geometry with coordination number nine. The Ln–S bond length is the longest value found in organolanthanide complexes containing the Ln–S bond up to now.