Dedicated to the memory of Professor Robert Vleggaar is investigated by means of cyclic voltammetry. The complexes all exhibit a twoelectron oxidation process that is W-based and a one-electron reduction that is mainly localized on the carbene ligand. Complexes 1-4 and 9-12 are considerably more difficult to oxidize than 5-8 due to the better π-acceptor ability of the (CO) 4 (PR' 3 ) (R' = Ph or OPh) ligand combination than that of (CO) 3 (dppe). Density functional theory calculations on the neutral, reduced and oxidized complexes confirmed the role of the frontier orbitals in the oxidation and reduction processes and enabled formulation of mathematical relationships that can be used to predict experimental measured potentials. X-ray crystal structures of 2cis, 3 and 5 are discussed.
In the title mononuclear coordination complex, [CuFe(C5H5)(C9H5F3O2)(C18H15P)2], the CuI ion is coordinated by the chelating β-diketonate 1-ferrocenyl-4,4,4-trifluorobutane-1,3-dione ligand through two O atoms and the two datively bonded triphenylphosphane ligands resulting in a distorted tetrahedral coordination sphere. The CuI ion, together with its chelating butane-1,3-dione group, is mutually coplanar [greatest displacement of an atom from this plane = 0.037 (1) Å], and the CuI ion lies slightly above [0.013 (1) Å] the plane. The overall geometry, including the bond distances and angles within the complex, corresponds to those of other reported copper(I) β-diketonates featuring organic groups at the β-diketonate ligand.
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