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Electronic Structures and Reduction Potentials of Cu(II) Complexes of [N,N′-Alkyl-bis(ethyl-2-amino-1-cyclopentenecarbothioate)] (Alkyl=Ethyl, Propyl, and Butyl)

  • Ricardo R. Contreras
  • Trino Suárez
  • Marisela Reyes
  • Fernándo Bellandi
  • Pedro Cancines
  • Jenny Moreno
  • Mona Shahgholi
  • Angel J. Di Bilio Bilio
  • Harry B. GrayEmail author
  • Bernardo Fontal
Chapter
Part of the Structure and Bonding book series (STRUCTURE, volume 106)

Abstract

Copper(II) complexes of N,N’-alkyl-bis(ethyl-2-amino-1-cyclopentenecarbodithioate) [alkyl=ethyl (L2), propyl (L3), and butyl(L4)] ligands have been synthesized and characterized. Analytical data for all three complexes show 1:1 copper-ligand stoichiometry. Well-resolved EPR spectra were recorded in toluene, benzene, and methylene chloride solutions at room temperature and in glassy toluene or toluene-methylene chloride mixtures in the range 20–150 K. The superhyperfine pattern unambiguously demonstrates coordination of two nitrogen atoms to copper; and the spin-Hamiltonian parameters [CuL2, g=2.115, A=187×10–4 cm–1; CuL3, g=2.128, A=165×10–4 cm–1; CuL4, g=2.138, A=147×10–4 cm–1] are as expected for a CuN2S2 coordination core. Quasi-reversible electrochemical behavior was observed in methylene chloride: the Cu(II)/Cu(I) reduction potentials increase from –1.17 V (E° vs Ag/AgNO3) for CuL2 to –0.74 V for CuL4, indicating greater stabilization of Cu(I) in CuL4. Taken together, these data demonstrate that lengthening the N,N′-alkyl chain distorts the planar CuN2S2 core (CuL2) toward a flattened tetrahedral geometry (CuL4).

Copper complexes Reduction potentials Electronic structures EPR spectra 

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Copyright information

© Springer-Verlag Berlin Heidelberg 2004

Authors and Affiliations

  • Ricardo R. Contreras
    • 1
  • Trino Suárez
    • 1
  • Marisela Reyes
    • 1
  • Fernándo Bellandi
    • 1
  • Pedro Cancines
    • 1
  • Jenny Moreno
    • 1
  • Mona Shahgholi
    • 2
  • Angel J. Di Bilio Bilio
    • 2
  • Harry B. Gray
    • 2
    Email author
  • Bernardo Fontal
    • 1
  1. 1.Laboratorio de Organometálicos, Departamento de Química, Facultad de CienciasUniversidad de Los AndesMérida
  2. 2.Beckman InstitutePasadena

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