The binuclear complex [Ag2(m-Ph2PNHPPh2)3](ClO4)2CH2Cl2CH3OH (Ph2PNHP- Ph2 = bis(diphenylphosphino)amine) was prepared from the reaction of AgClO4 with bis- (diphenylphosphino)amine in equimolar ratio through self-assembly. The coordination cation affords a triply-bridging [Ag2L3]-type coordination moiety. The silver atom is in a trigonal planar environment with P3 coordination chromophore. The complex (C74H69Cl4N3O9P6Ag2) crystallizes in monoclinic, space group Cc with a = 18.3738(1), b = 20.0207(4), c = 20.5422(4) ? b = 95.829(1), V = 7517.5(2) 3, Z = 4, Mr = 1687.68, Dc = 1.491 g/cm3, F(000) = 3432, m = 0.848 mm-1, the final R = 0.0460 and wR = 0.0935 for 7005 observed reflections with I > 2s(I).
The reaction between [Cu2(m-dppm)2(MeCN)4](ClO4)2(dppm = bis(diphenylphos- phino)methane) and [Zn(PhS)2(bpy)] (bpy = 2,2-bipyridine, PhS = benzenethiolate) gave the complex [Cu2(m-dppm)2(m-PhS)(MeCN)]ClO40.5(Et2O)(C58H52ClNO4P4SCu20.5Et2O) which was determined by X-ray single-crystal diffraction. The crystal is of orthorhombic, space group P212121 with a = 13.6157(3), b = 20.8022(6), c = 21.3299(6) ? V = 6041.4(3) 3, Mr = 1182.54, Dc = 1.300 g/cm3, F(000) = 2444, m = 0.934 mm-1 and Z = 4. The final R = 0.0773 and wR = 0.1843 for 7744 observed reflections (I > 2s(I)). The dicopper atoms are doubly bridged by dppm as well as one S donor from benzenethiolate. One copper atom is in a distorted trigonal bipyramidal environ- ment, whereas the other adopts a distorted tetrahedral geometry.
The synthesis and crystal structure of oxo-centered carboxylate-bridge trinuclear ruthenium complex, Ru3O(CH3COO)6(py)2Cl (py = pyridine) (1), are reported herein. The complex 1 has been characterized by IR, cyclic voltammetry (CV), UV-Vis and X-ray crystal analysis. The complex 1 in 0.1 mol/L (n-C4H9)4NPF6-CH2Cl2 solution at room temperature shows four one- electron redox processes at E1/2 = -1.38, -1.20, -0.17 and 1.07 V vs. Ag/AgCl.
The reaction between [Mn(bpy)2(MeOH)2](SbF6)2 (bpy = 2,2-bipyridine) and (Et4N)[Ni(pymt)3] (pymt = pyrimidine-2-thiolate) gave the complex [Ni(bpy)2(pymt)](SbF6) which was determined by X-ray single-crystal diffraction. The structure is of monoclinic with space group C2/c, a = 25.190(2), b = 11.3178(7), c = 19.296(1) ? b = 101.364(1)? V = 5393.4(6) 3, Mr = 718.98, Dc = 1.771 g/cm3, F(000) = 2840, m = 1.845 mm-1 and Z = 8. The final refinement gave R = 0.0641 and wR = 0.1399 for 3598 observed reflections (I > 2s(I)). The nickel(Ⅱ) atom is coordinated by four N donors from two bpy in the cis-conformation and two other atoms of S and N from one pymt, forming a distorted coordination octahedron.
Self-organization of copper (I) ion with bridging ligand bis(diphenylphosphino)-acetylene resulted in the isolation of a dinuclear copper ( I ) complex [Cu2(μ-Ph2PC≡ CPPh2)3(MeCN)2](ClO4)2·Et2O. Structural analysis indicated the existence of a helical coordination cage, in which two copper (I) atoms are bridged triply by the linear diphosphine Ph2PC≡CPPh2 with the CuACu separation of 6.231 A. The copper (I) atom is in an approximately tetrahedral environment with a NP3 coordination chromophore. The complex crystallizes in the triclinic, space group P 1 with a = 13.8456(2), b = 16.6010(1), c = 18.9215(3) A, α = 98.289(1), β = 91.232(1), γ = 106.496(1)°, V = 4117.60(9) A3, Z = 2, C86H82Cl2N2O9P6Cu2, Mr= 1659.37, Dc= 1.338 g/cm3, F(000) = 1708, μ = 0.754 mm-1, the final R = 0.0688 and wR = 0.1940 for 11692 reflections with I>2σ(I).
HAN Lei ZHANG Li-Yi CHEN Zhong-Ning HONG Mao-Chun(State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, The Chinese Academy of Sciences, Fuzhou, Fujian 350002, China)
The heterotrinuclear complex [PtCu2(m-dppm)2(dmbpy)2(m-h1,h2 C CPhCH3-4)2] (ClO4)21.5CH2Cl2 1 (dmbpy = 4,4-dimethyl-2,2?bipyridine, dppm = bis(diphenylphosphino)meth- ane) has been prepared and characterized by X-ray crystallography. The complex crystallizes in the triclinic system, space group P with a = 12.9359(3), b = 14.3908(2), c = 15.2121(3) ? α = 107.370(1), β = 93.539(1), γ = 108.207(1), V = 2529.59(8) ?, Mr = 2015.96, Z = 1, Dc = 1.323 g/cm3, F(000) = 1019, m(MoKa) = 2.042 mm-1, the final R = 0.0604 and wR = 0.1529 for 8002 observed reflections with I > 2σ(I). The 4-methylphenylacetylides are bonded to the PtII and CuI centers in η1 (s) and η2 (p) coordination modes, respectively. The PtII atom is linked by one dppm bridge to adopt a square planar environment and CuI by one alkynyl ligand to assume a distorted tetrahedral geometry.
A novel dimeric complex [Ru3 (μ3-O)(μ-CH3COO)(CO)]2(μ-dppf)(μ-odppf)(dppf = 1, 1'-bis(diphenylphosphio)ferrocene, odppf = 1, 1'-bis(oxodiphenylphosphoranyl)ferrocene) (1) of oxo-centered triruthenium-aectate cluster units was synthesized and characterized by X-ray crystallography. Compound 1 exhibits a cyclic structure formed by linkages of two triruthenium cluster units Ru3 (μ3-O)(μ-CH3COO)6(CO) through dppf and odppf ligands, respectively. The diameter of the molecular loop is ca. 1.0 nm.
