Copper(I) complexes, copper(I)/O2 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, J. Zubieta, K. D. Karlin

Research output: Contribution to journalArticlepeer-review

170 Scopus citations

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)ClO4, the copper(I) complexes [Cu(pmea)]PF6 (1b-PF6), [Cu(pmap)]PF6 (1c-PF6), and copper(II) complexes [Cu(pmea)Cl]ClO4·H2O (2b-ClO4·H2O), [Cu(pmap)Cl]ClO4·H2O (2cClO4·H2O), [Cu(pmap)Cl]ClO4 (2c-ClO4), and [Cu(pmea)F]2(PF6)2 (3b-PF6) were determined. Crystal data: H(tepa)ClO4, formula C21H25ClN4O4, 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-PF6, formula C19H20CuF6N4P, 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-PF6), formula C20H22CuF6N4P, 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-ClO4·H2O, formula C19H22Cl2CuN4O5, 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-ClO4·H2O, formula C20H24Cl2CuN4O5, monoclinic space group P21/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-ClO4, formula C20H22Cl2CuN4O4, monoclinic space group P21/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-PF6, formula [C19H20CuF7N4P]2, monoclinic space group P21/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)(CH3CN)]+ (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-PF6, 1b-PF6, and 1c-PF6 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

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint Dive into the research topics of 'Copper(I) complexes, copper(I)/O<sub>2</sub> reactivity, and copper(II) complex adducts, with a series of tetradentate tripyridylalkylamine tripodal ligands'. Together they form a unique fingerprint.

Cite this