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Reactions of [NH4]2[MS4](M = Mo,W), CuX(X = Br, I) and PPh3 in the solid state produced four mixed-metal sulfur containing clusters {Cu3MS3X}(PPh3)3S(M = Mo, W; X = Br, I), two of which (1: M = Mo, X = I; 2: M = W, X = Br) were structurally determined. Crystals of 1 and 2 are triclinic, space group P1 (1: a = 11.895(3), b = 13.107(1), c = 20.473(2)A, α = 74.95(6), β = 84.87(8), γ = 64.27(7)°, Z=2, V=2776.1 A3, Rw = 0.064 for 6443 observed reflections. 2: a = 11.876 (1), b = 13.065 (2), c = 20.325(2)A, α = 74.95(1), β= 85.39(1), γ = 64.09(1)°, Z = 2, V = 2737.3A3, Rw = 0.055 for ·5303 observed reflections). The results of the structure determination showed that the central units of the two cubane-like cluster compounds are composed of four metal atoms and four non-metal atoms situated at alternate corners. The differences of cubane-like cluster compounds obtained from solid state reactions and from solution reactions are discussed.

A polynuclear complex containing a monomer of Cu(II)-Zn(II) heterobinuclear unit was synthesized and characterized by IR spectra and magnetic moment. The crystal and molecular structure of the complex, CuZnC19H24Cl4N2O2, was determined by X-ray diffraction, it crystallized in monoclinic, P21/m, α = 8.812 (2), b = 15.972(3), c = 8.831(1) A, β = 114.33(1)°, V = 1132.4A3, Z = 2, De = 1.710 g/ cm3,γ(MoKα) =0.71073 a, μ = 25.227 cm−1, R = 0.051. Rw = 0.063 for 1130 observed reflections with I>3α(1). The coordinated octahedra of Cu(II) and tetrahedra of Zn(II) via bridging CI atoms form a single chain polynuclear complex. The Cu, Zn and bridging Cl atoms are located on the crystallographic symmetry plane m which is perpendicular to 2N and 2O donor plane.

The reaction of TbCl3 with K[2,4-(CH3)2 C5H5] at 0°C in THF followed by crystallization at −90°C led to a pale yellow hexagonal prismatic crystalline product [2,4-[CH3)2-η5-C5H5]3-Tb·1/2THF, which is highly sensitive to air and water and rapidly efflorescent at ambient temperature. The single crystal X-ray diffraction data of the compound have been collected at low temperature (-60°C) and the crystal structure has been solved by heavy atom method. It belongs to triclinic system, space group P1 with lattice parameters α=8.477 A, b=12.583 A, c=12.858 A, α=118.08°, β=91.38°, γ=108.75°, V=1120.36 A3 and Z=2. Least-squares refinement converged to a final value R=0.043. The compound possesses an idealized C3h symmetry with three 2,4dimethylpentadienyl ligands bound to the central terbium atom in a pentahapto mode (η5). Each unit cell contains two molecules of [2,4-(CH3)2-η5-C5H5]3Tb and one molecule of solvent THF, of which the role in the lattice has been discussed in detail.

Two title nido-11-vertex platinaundecaboranes, 7,7-bis-(triphenylphosphine-P)-8, 10-diethoxy-8, 9:10, 11-bis-μ-H-7-platina-nido-undecaborane-dichloromethane (I) and 7,7-bis-(triphenylphosphine-P) -8, 10-di(i-propoxy) -8,9:10,11-bis-μ-H-7-platina-nido-undecaborane (II), were prepared and their structures were determined by single crystal X-ray diffraction method. Each of them has an 11-vertex nido-polyhedral skeleton. {PtB10} cage is substituted by two ethoxy or i-propoxy groups at 8 and 10 positions, respectively.

The title platinaborane, [(P(2)Ph3)Pt(l)(μ2-B(11)-(B(9)-OC-(CH3)3-B10H10)Pt(7)(P(1)Ph3)]2, a triple cluster, which is a binuclear Pt complex dimmer, was prepared. Single crystal X-ray diffraction analysis shows that a Pt(7) atom served as a common vertex between cluster |PtB10| and |Pt4|. The |Pt4| cluster is of parallelogram.