Isotopic labeling investigation of the oxygenation of nickel-bound thiolates by molecular oxygen Academic Article uri icon


  • Discrete compounds resulting from the oxidation and oxygenation of nickel thiolate complexes have been isolated, separated, and characterized. Molecular oxygen or hydrogen peroxide reacted with [N,N′-bis(mercaptoethyl)-1,5-diazacyclooctane] nickel(II), (BME-DACO)NiII (1), to produce two oxygenates, [(mercaptoethyl)(sulfinatoethyl)diazacyclooctane] nickel(II), (MESE-DACO)NiII (2), and [bis(sulfinatoethyl)diazacyclooctane]nickel(II), (BSE-DACO)NiII (3), as well as a trimetallic, [(BME-DACO)Ni]2Ni2+ (4). Matrix-assisted laser desorption (MALD) ionization was used to obtain Fourier transform ion cyclotron resonance (FT-ICR) mass spectra on isotopomers of 2 and 3. Isotopic labeling experiments (18O2/16O2 mixtures) demonstrated that both oxygens in the sulfinate ligand of 1 were derived from the same dioxygen molecule. The molecular structures of 2 and 4 were determined by X-ray crystallography. Crystallographic data are given as a, b, c; β space group, Z, 2θ range, unique observed reflections, R(Rw) (%). (MESE-DACON)NiII: 8.306 (3), 12.258 (3), 12.773 (4) Å; 101.36 (3)°, P21/n, 4, 4.0°/50.0°, 2047 (I> 2.0σ(I)), 2.85 (3.61). {[BME-DACO)Ni]2Ni}(Br2: 7.144 (2), 10.931 (2), 17.296 (3) Å; 91.72 (2)°, P21/c, 4, 4.0°/50.0°, 2053 (I > 2.0 σ(I)), 4.46 (4.84). The pseudo-square-planar NiN2S2 complex 2 has cis sulfur donor atoms and a tetrahedral twist of 18.4°. The Ni—Ssulfinato distance of 2.140 (1) Å is significantly shorter than the Ni—Sthiolate distance, 2.163 (1) Å. The trimetallic 4 contains a staircaselike structure where two molecules of 1 serve as metallothiolate ligands to the central Ni2+ creating an NiS4 square plane (dihedral angle between best square planes = 103.4°). © 1992, American Chemical Society. All rights reserved.

published proceedings

  • Journal of the American Chemical Society

author list (cited authors)

  • Farmer, P. J., Solouki, T., Mills, D. K., Soma, T., Russell, D. H., Reibenspies, J. H., & Darensbourg, M. Y

citation count

  • 117

complete list of authors

  • Farmer, Patrick J||Solouki, Touradj||Mills, Daniel K||Soma, Takako||Russell, David H||Reibenspies, Joseph H||Darensbourg, Marcetta Y

publication date

  • June 1992