Copper(I) complexes, copper(I)/O 2 reactivity, and copper(II) complex adducts, with a series of tetradentate tripyridylalkylamine tripodal ligands

M. Schatz, M. Becker, F. Thaler, F. Hampel, S. Schindler, R. R. Jacobson, Z. Tyeklár, N. N. Murthy, P. Ghosh, Q. Chen, Jon A Zubieta, K. D. Karlin

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Abstract

Copper(I) and copper(II) complexes possessing a series of related ligands with pyridyl-containing donors have been investigated. The ligands are tris(2-pyridylmethyl)amine (tmpa), bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine (pmea), bis[2-(2-pyfidyl)ethyl]-(2-pyridyl)methylamine (pmap), and tris[2-(2-pyridyl)ethyl]amine (tepa). The crystal structures of the protonated ligand H(tepa)ClO 4, the copper(I) complexes [Cu(pmea)]PF 6 (1b-PF 6), [Cu(pmap)]PF 6 (1c-PF 6), and copper(II) complexes [Cu(pmea)Cl]ClO 4·H 2O (2b-ClO 4·H 2O), [Cu(pmap)Cl]ClO 4·H 2O (2cClO 4·H 2O), [Cu(pmap)Cl]ClO 4 (2c-ClO 4), and [Cu(pmea)F] 2(PF 6) 2 (3b-PF 6) were determined. Crystal data: H(tepa)ClO 4, formula C 21H 25ClN 4O 4, triclinic space group P1̄, Z = 2, a = 10.386(2) Å, b = 10.723(2) Å, c = 11.663(2) Å, α = 108.77(3)°, β = 113.81(3)°, γ = 90.39(3)°; 1b-PF 6, formula C 19H 20CuF 6N 4P, orthorhombic space group Pbca, Z = 8, a = 14.413(3) Å, b = 16.043(3) Å, c = 18.288(4) Å, α = β = γ = 90°; (1c-PF 6), formula C 20H 22CuF 6N 4P, orthorhombic space group Pbca, Z = 8, a = 13.306(3) Å, b = 16.936(3) Å, c = 19.163(4) Å, α = β = γ = 90°; 2b-ClO 4·H 2O, formula C 19H 22Cl 2CuN 4O 5, triclinic space group P1̄, Z = 4, a = 11.967(2) Å, b = 12.445(3), Å, c = 15.668(3) Å, α = 84.65(3)°, β = 68.57(3)°, γ = 87.33(3)°; 2c-ClO 4·H 2O, formula C 20H 24Cl 2CuN 4O 5, monoclinic space group P2 1/c, Z = 4, a = 11.2927(5) Å, b = 13.2389(4) Å, c = 15.0939(8) Å, α = γ = 90°, β = 97.397(2)°; 2c-ClO 4, formula C 20H 22Cl 2CuN 4O 4, monoclinic space group P2 1/c, Z = 4, a = 8.7682(4) Å, b = 18.4968(10) Å, c = 13.2575(8) Å, α = γ = 90°, β = 94.219(4)°; 3b-PF 6, formula [C 19H 20CuF 7N 4P] 2, monoclinic space group P2 1/n, Z = 2, a = 11.620(5) Å, b = 12.752(5) Å, c = 15.424(6) Å, α = γ = 90°, β = 109.56(3)°. The oxidation of the copper(I) complexes with dioxygen was studied. [Cu(tmpa)(CH 3CN)] + (1a) reacts with dioxygen to form a dinuclear peroxo complex that is stable at low temperatures. In contrast, only a very labile peroxo complex was observed spectroscopically when 1b was reacted with dioxygen at low temperatures using stopped-flow kinetic techniques. No dioxygen adduct was detected spectroscopically during the oxidation of 1c, and 1d was found to be unreactive toward dioxygen. Reaction of dioxygen with 1a-PF 6, 1b-PF 6, and 1c-PF 6 at ambient temperatures leads to fluoride-bridged dinuclear copper(II) complexes as products. All copper(II) complexes were characterized by UV-vis, EPR, and electrochemical measurements. The results manifest the dramatic effects of ligand variations and particularly chelate ring size on structure and reactivity.

Original languageEnglish (US)
Pages (from-to)2312-2322
Number of pages11
JournalInorganic Chemistry
Volume40
Issue number10
DOIs
StatePublished - May 7 2001

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ASJC Scopus subject areas

  • Inorganic Chemistry

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Schatz, M., Becker, M., Thaler, F., Hampel, F., Schindler, S., Jacobson, R. R., Tyeklár, Z., Murthy, N. N., Ghosh, P., Chen, Q., Zubieta, J. A., & Karlin, K. D. (2001). Copper(I) complexes, copper(I)/O 2 reactivity, and copper(II) complex adducts, with a series of tetradentate tripyridylalkylamine tripodal ligands. Inorganic Chemistry, 40(10), 2312-2322. https://doi.org/10.1021/ic000924n