Syntheses and crystal structures of polynuclear Cu(I) complexes containing the 1,1 '-bis(diphenylphosphino)-ferrocene ligand

Citation:
Pinto, P., M. J. Calhorda, V. Felix, T. Aviles, and M. G. B. Drew. "Syntheses and crystal structures of polynuclear Cu(I) complexes containing the 1,1 '-bis(diphenylphosphino)-ferrocene ligand." Monatsh Chem. 131 (2000): 1253-1265. copy at https://docentes.fct.unl.pt/p387/publications/syntheses-and-crystal-structures-polynuclear-cui-complexes-containing-11-bisdiphen

Abstract:

The reaction between [Cu(NCMe)(4)][PF6] and 1,1'-bis-(diphenylphosphino)-ferrocene (dppf) in several ratios, solvents, and conditions led to the synthesis and structural characterization of the Cu(I) complexes [Cu(dppf)(Odppf)] [PF6] (1), [(dppf)Cu(mu -dppf)Cu(dppf)][PF6](2) (2), and [(dppf)Cu(mu -Cl)(2)Cu(dppf)] (3). Although 1 and the cation in 2 were known, the first was structurally characterized for the first time, exhibiting a significant asymmetry in the coordination sphere of Cu(I)) owing to the presence of oxygen. In 2, the PF6- anion led to an interesting crystal packing with large open channels containing water. Finally, DFT calculations on a model of 3 showed that its HOMO exhibits, besides Fe, a significant Cu and Cl character, which is reflected in its electrochemical properties.

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