Oleg S. Chudin

New trinuclear μ3-vinylidene cluster CpReFePt(μ3-C=CHPh)(CO) 5 [P(OPr i ) 3 ] 2

The X-ray diffraction study of a new heterometallic cluster CpReFePt(μ3-C=CHPh)(CO)5[P(OPri)3]2 is performed. The crystallographic characteristics are as follows: a = 11.0275(4) Å, b = 33.0367(12) Å, c = 12.2691(5) Å, β = 98.3660(10)°, V = 4422.2(3) Å3, space group P21/n, Z = 4, dcalc = 1.744 g/cm3. The cluster contains the phenylvinylidene ligand coordinated with a trimetallic core in the form of a Re–Fe–Pt chain (the Re–Fe and Fe–Pt bond lengths are 2.794(7) Å and 2.628(1) Å respectively; the Re···Pt distance is 3.354(1) Å).

Structure of a trinuclear μ 3 -vinylidene cluster CpMnFePt(μ 3 -C=CHPh)(PPh 3 )(CO) 6

The single crystal X-ray diffraction study of the heterometallic cluster CpMnFePt(μ3-C=CHPh)(PPh3)(CO)6 is performed. The crystallographic characteristics are as follows: a = 32.356(15) Å, b = 11.754(5) Å, c = 20.114(9) Å, β = 115.707(6)°, V = 6893(5) Å3, space group C2/c, Z = 8, dcalc = 1.741 g/cm3. The cluster molecule contains a bridging phenylvinylidene ligand coordinated to a metallic core in the form of a Mn–Fe–Pt chain (the Mn–Fe and Fe–Pt bond lengths are 2.6768(14) Å and 2.6280(11) Å respectively and the Mn⋯Pt distance is 3.6425(19) Å).

Electrochemical Study of Phenylvinylidene Clusters Containing ReFePt Metal Cores and Chelate Diphosphine Ligands

The redox transformations of trinuclear phenylvinylidene CpReFePt(μ3-C=CHPh)(CO)5(P-P) [Cpcyclopentadienyl; P-P – 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino) propane] clusters were studied by electrochemical methods at platinum, glassed carbon, and dropping mercury electrodes in acetonitrile solutions. It was established that one-electron oxidation of the clusters results in formation of the binuclear Cp(CO)2RePt(μ-C=CHPh)(P-P) [P-P = dppe, dppp] complexes and Fe-containing fragments.

Crystal structure of μ-carbonyl-1:2κ2C:C-carbonyl-1κC-(1η5-cyclo­penta­dien­yl)iodido-2κI-[μ-2-(pyridin-2-yl)ethene-1,1-diyl-1κC1:2κ2N,C1]ironpalladium(Fe—Pd) benzene monosolvate

The title binuclear μ-pyridylvinylidene FePd complex (FePd1) was obtained from Cp(CO)2FeI and 2-ethynylpyridine in diisorpopylamine in the presence of PdCl2

Redox Properties of Binuclear Rhenium-Platinum Vinylidene Complexes with Phosphorus Containing Ligands

The redox properties of new binuclear μ-vinylidene complexes Cp(CO)2RePt(μ-C = C2HPh)LL′ [L = СO, L′ = PPh3 (1); L = СO, L′ = P(OPr)3 (2); L = L′ = PPh3 (3); L = L′ = P(OPr)3 (4)] were studied by electrochemical methods at a platinum, a glassed carbon and a dropping mercury electrodes in acetonitrile solutions. It was established that one-electron oxidation of 3 and 4 results in a cleavage of the Re-Pt and Pt-C1 bonds affording vinylidene complex Cp(CO)2RePt = C = CHPh and [PtLL′] fragments. In contrast to complexes 3 and 4, one-electron oxidation of 1 and 2 is reversible, indicating the greater electrochemical stability of lasts relative to 3 and 4.