Ruina Yang

Synthesis of asymmetric binuclear copper(I) complexes containing 4-vinylpyridine and bis(diphenylphosphino) methane

The asymmetric binuclear copper(I) complex [Cu2(dppm)2(C7H7N)(μ-NO3)](NO3) (dppm = Ph2PCH2PPh2, C7H7N = 4-vinylpyridine) has been prepared and characterized. The complex is photoluminescent at room temperature. Crystals are triclinic space group , with cell parameters a = 11.638(2), b = 12.621(3), c = 18.516(4) Å, α = 89.20(3), β = 83.11(3), γ = 76.04(3)°, V = 2619.5(9) Å3, D c = 1.426 g cm−3, Z = 2, μ = 0.988 mm−1, R = 0.0497 for 6574 independently observed reflections with I > 2σ(I). The structure consists of [Cu2(dppm)2(C7H7N)(μ-NO3)]+ cations and nitrate anions. Copper atoms show different coordination modes; Cu(2) has a distorted trigonal and Cu(1) a tetrahedral geometry.

Synthesis of a binuclear copper(I) complex [Cu2(PPh3)6(k-OOCH)](ClO4) – insertion reaction of carbon dioxide

A novel binuclear complex [Cu2(PPh3)6(μ-OOCH)](ClO4) (II) was synthesized via the interaction of carbon dioxide with [Cu(PPh3)2(BH4)] (I) in the presence of PPh3 and NBu4(ClO4). It was characterized by elemental analysis and spectroscopic methods as well as by single-crystal X-ray diffraction. Crystals are monoclinic, space group C 2/c, with a = 25.911(5), b = 13.6361(3), c = 26.929(5) Å, β = 90.21(3)°, V = 9323.1(3) Å3, Z = 8 and D c = 1.314 g cm−3. The formate ligand of II in the solid state displays a near-perfect linear coordination mode as CO2 and serves as a bridge for the two Cu(PPh3)3 units with the O–C–O bond angle being 180.0(5)°. A mechanism involving carbon dioxide insertion into the Cu–H bond of [Cu(PPh3)2(BH4)] (I) for the formation of II is proposed.