Issue 27, 2013

Tuning affinity and reversibility for O2 binding in dinuclear Co(ii) complexes


The O2 binding affinity of a series of dicobalt(II) complexes can be tuned between p(O2)50% = 2.3 × 10−3 and 700 × 10−3 atm at 40 °C by varying the number of H and Cl atoms in the bridging acetato ligands of [Co2(bpbp)(CH(3−n)ClnCO2)(CH3CN)2]2+, where bpbp = 2,6-bis(N,N-bis(2-pyridylmethyl)aminomethyl)-4-tert-butylphenolate and n = {0, 1, 2, 3}. O2 binds most strongly to the deoxy complex containing the acetato bridge and the O2 affinity decreases linearly as the number of Cl atoms is increased from 0 to 3 in [Co2(bpbp)(O2)(CH3CO2)]2+, [Co2(bpbp)(O2)(CH2ClCO2)]2+, [Co2(bpbp)(O2)(CHCl2CO2)]2+ and [Co2(bpbp)(O2)(CCl3CO2)]2+. The O2 affinities can be qualitatively correlated with both the pKa value of the parent acetic or chloroacetic acid and the redox potential of the O22−/O2˙ couple measured for the peroxide-bridged complexes. The redox potential varies between 510 mV (vs. Fc0/+) for the acetato-bridged complex to 696 mV for the trichloroacetato-bridged system. Despite the clear difference in reactivity in solution, there are no clear trends which can be correlated to O2 affinity in the O–O bond lengths in the X-ray crystal structures at 180 K (1.415(4)–1.424(2) Å) or in the frequencies of the peroxido O–O stretch in the solid-state resonance Raman spectra at 298 K (830–836 cm−1). Using density functional theory calculations, we conclude that the Co(II) atoms of the deoxy complexes coordinate solvent molecules as auxiliary ligands and that a conformation change of the ligand is involved in the reversible O2 binding process. The alternative of five coordination in the deoxy Co(II) complexes is therefore seen as less likely. The crystal structure and p(O2)50% are also reported for the 1-naphthoato-bridged oxy complex [Co2(bpbp)(O2)(C10H7O2)]2+, and the O2 binding affinity in that case is also qualitatively consistent with the expectation from the pKa of the parent 1-naphthoic acid.

Graphical abstract: Tuning affinity and reversibility for O2 binding in dinuclear Co(ii) complexes

Supplementary files

Article information

Article type
06 Mar 2013
04 May 2013
First published
09 May 2013
This article is Open Access
Creative Commons BY license

Dalton Trans., 2013,42, 9921-9929

Tuning affinity and reversibility for O2 binding in dinuclear Co(II) complexes

M. S. Vad, F. B. Johansson, R. K. Seidler-Egdal, J. E. McGrady, S. M. Novikov, S. I. Bozhevolnyi, A. D. Bond and C. J. McKenzie, Dalton Trans., 2013, 42, 9921 DOI: 10.1039/C3DT50617G

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