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A series of luminescent polynuclear copper(I) phenyl thiolate clusters with functional groups in the organic ligand shell has been synthesized and characterized by single-crystal X-ray diffraction. Cluster compounds 1- 5 with Me2N groups bound to the phenyl thiolate are described and feature different nuclearities and core geometries. The heptanuclear compound 6, which contains both phenyl thiolate and Me3SiO functionalized phenyl thiolate ligands, is an unusual example of a mixed thiolate cluster and exhibits a core almost identical to that of 5. The optical properties of these compounds, which range from binuclear complexes with large Cu ···Cu distances to cluster molecules with seven copper atoms and relatively short Cu ···Cu distances, have been investigated. Compounds 1- 5 show strong absorption below 500 nm. The intense luminescence covers a wide range of the visible spectrum ( 1: green; 2 and 3: blue; 4 and 5: yellow). It seems likely that the optical transitions occur between orbitals of the thiol ligands and metal-centered orbitals; for the species with short Cu ···Cu distances ( 3- 5), these interactions cause a further redshift of the spectra. In addition, the influence of functional groups on optical absorption and emission is shown by the two Cu7 clusters 5 and 6, which differ solely in the electron-donating nature of their functional groups. [ABSTRACT FROM AUTHOR]

Abstract: Treatment of tetraphosphonitoresorcinarene [(CH3)2CHCH2CHC6H2O2PPh]4 (1) with an excess [CuCl] powder in the presence of pyridine (py) yielded a tetracopper(I) phosphonitocavitand [pyH][1·Cu4(μ-Cl)4(μ 4-Cl)] (2). The Included μ 4-Cl in 2 was easily substituted by heavy halide anion to give [pyH][1·Cu4(μ-Cl)4(μ 4-X)] (X=Br, 3; I, 4). The complexes 2, 3, and 4 have been characterized by X-ray structure determinations. The similar structure contains four coplanar cupper atoms bridged by four μ-Cl and one central trapped μ 4-X atoms in the inside of the closing bowl-shaped cavitand. The third-order nonlinear optical properties of 2 as a typical metal-cavitand complex were investigated in this paper. [Copyright &y& Elsevier]

Three novel η 3 -2-azaallyl iron(I) complexes, [(2-PPh 2 )C 6 H 4 ](CH=N-CH)C 6 H 4 (4-R)]Fe(PMe 3 ) 2 ( 4 - 6 ) (R = H ( 4 ), Cl ( 5 ) and OMe ( 6 )), were prepared through the reactions of Schiff base preligands [(2-PPh 2 )C 6 H 4 ](CH=NCH 2 )C 6 H 4 (4-R)] ( 1 - 3 ) (R = H ( 1 ), Cl ( 2 ) and OMe ( 3 )) with Fe(PMe 3 ) 4 via sp 3 C-H bond activation under mild reaction conditions. Compared with the reported 2-azaallyl cobalt complexes, these are the first 2-azaallyl iron(I) complexes obtained via Csp 3 -H bond activation. Complex [(2-PPh 2 )C 6 H 4 ](CH=N-CH) (C 6 H 4 )FeBr(PMe 3 ) 2 ( 7 ) was obtained through the reaction of 4 with EtBr. The ligand replacement reaction of complex 4 with CO delivered the dicarbonyl iron(I) complex [(2-PPh 2 )C 6 H 4 ](CH-N=CH) (C 6 H 5 )Fe(CO) 2 (PMe 3 ) ( 8 ). The molecular structures of complexes 4 and 6 were determined by single crystal X-ray diffraction. [ABSTRACT FROM AUTHOR]

Three diorganocobalt chlorides [CoClMe(PMe3)2-{(C5H6)- CH=O}] (4), [CoClMe(PMe3)2-{(C6H8)-CH=O}] (5), and [CoClMe(PMe3)2-{(C6H7Memeta)-CH=O}] (6) were synthesized through cyclometalation reactions with aldehyde as an anchoring group involving aliphatic vinylic C-Cl bond activation. Complexes 4-6 were characterized by IR and NMR spectroscopy. The crystal and molecular structures of complexes 4 and 5 were determined by single-crystal X-ray diffraction. Complexes 4-6 are stable in solution at room temperature, but they decompose at above 30°C affording C,C-couplings products with the formation of [Co(PMe3)3Cl]. The results of this work will be important for people to deepen the understanding of the C-Cl bond activation mechanism. [ABSTRACT FROM AUTHOR]

Abstract: Interaction of Ag(CF3CO2) with bis(diphenylphosphino)amide (dppa) in THF gave a tetranuclear Ag4-coplanar silver(I) complex [Ag4(μ-dppa)2(μ4-O2PPh2)2(μ-CF3CO2)2] (1). The trinuclear trigonal-bipyramid copper(I) complex [Cu3(μ3-Cl)2(μ-dppa)3][CuCl2] (2) was obtained from the reaction of [CuCl] powder with bis(diphenylphosphino)amide (dppa) in THF. Treatment of 2 with (Me3Si)2Se in THF afforded a μ8-selenide-centered octanuclear copper(I) complex [Cu8(μ8-Se)(μ4-Se)(μ4-SeH)3(μ-dppa)4][(Ph2PO)2N] (3). The structures of 1–3 were determined by single-crystal X-ray diffraction analyses. Complex 1 comprises a rectangular Ag4 array with each edge bridged with a pair of μ-dppa, μ4-O2PPh2 and μ-CF3CO2 ligands that are approximately perpendicular to each other. Complex 2 contains a trigonal-bipyramid [Cu3(μ3-Cl)2]+ core surrounded by three μ-dppa ligands. The cationic complex in 3 consists of four [Cu2(μ-dppa)] fragments side-capped by one μ4-Se and three μ4-SeH ligands and center-connected by a μ8-Se atom. [Copyright &y& Elsevier]

Abstract: Reaction of the ammonium salt of keplerate, [{(MoVI)MoVI 5O21(H2O)6}12{MoV 2O4CH3COO)}30]42– with Gd(NO3)3 leads to complex transformations with [{Gd(H2O)5}4{Mo36(NO)4O108(H2O)16}]·34 H2O (1) as final product. According to X-ray structural data it contains anions [Mo36(NO)4O108(H2O)16]12–, cross-linked into a neutral 2D-framework by Gd3+ ions. To cite this article: N.V. Izarova et al., C. R. Chimie 8 (2005) . [Copyright &y& Elsevier]

Abstract: Two new Re(III) and Re(IV) complexes with 2(2′-pyridyl)benzimidazole (pbimz) were prepared and their crystal and molecular structures established by single-crystal X-ray diffraction. Reaction of [ReOCl2(OEt)(PPh3)2] with the ligand gave red cis(Cl),trans(P)-[ReCl2(PPh3)2(pbimz)]Cl (1), while red [ReCl4(pbimz)]·OPPh3 (2) was obtained from [ReCl3(PhC(O)C(O)Ph)(PPh3)] and pbimz in the presence of perchlorate. The compounds were characterized by elemental analysis, FAB-MS, UV–Vis, IR, NMR spectroscopy and magnetic susceptibility measurements. [Copyright &y& Elsevier]

Abstract: A new metal–organic coordination polymer [Fe(4,4′-bpy)3(H2O)2](PF6)2·2(4,4′-bpy)·5 H2O (1) (bpy = bipyridine) was prepared. X-ray structural analysis reveals that 1 is a three-dimensional network with nanosized channels constructed from one-dimensional coordination chains via non-covalent interactions between the pyridile rings. The channels clathrate large molecules of free 4,4′-bpy. Magnetic susceptibility measurement confirms the presence of isolated high-spin Fe(II) in 1. To cite this article: N. V. Izarova et al., C. R. Chimie 8 (2005). [Copyright &y& Elsevier]