Jump to main content
Jump to site search

Issue 42, 2011
Previous Article Next Article

How molecular oxygen binds to bis[trifluoroacetylacetonato(−1)]cobalt(ii) – ab initio and density functional theory studies

Author affiliations

Abstract

Cobalt(II) diketonate complexes, such as bis[trifluoroacetylacetonato(−1)]cobalt(II) [Co(tfa)2], catalyze the aerobic oxidation of alkenols into functionalized tetrahydrofurans. To gain insight into activation of triplet dioxygen by Co(tfa)2 in a protic solvent, as used in oxidation catalysis, the electronic structure of aquabis[trifluoroacetylacetonato(−1)]cobalt(II)—Co(tfa)2(H2O)—and the derived dioxygen adduct were characterized using ab initio (CASSCF, NEVPT2) and density functional theory (BP86, TPSSh, B3LYP) methods. The ground state of Co(tfa)2(H2O) is a high-spin, quartet state. As dioxygen approaches the cobalt atom, the quartet state couples with a triplet dioxygen molecule and forms a sextet, a quartet, and a doublet spin state with the high-spin state being the lowest in energy. At the equilibrium Co–O2 distance of 1.9 Å, Co(tfa)2(H2O)(O2) has a doublet superoxo Co(III) ground state with the unpaired electron residing on the oxygen moiety, in a nearly unchanged O2 π* orbital.

Graphical abstract: How molecular oxygen binds to bis[trifluoroacetylacetonato(−1)]cobalt(ii) – ab initio and density functional theory studies

Back to tab navigation

Supplementary files

Article information


Submitted
20 Apr 2011
Accepted
15 Jun 2011
First published
28 Jul 2011

Dalton Trans., 2011,40, 11289-11295
Article type
Paper

How molecular oxygen binds to bis[trifluoroacetylacetonato(−1)]cobalt(II) – ab initio and density functional theory studies

A. Kubas, J. Hartung and K. Fink, Dalton Trans., 2011, 40, 11289
DOI: 10.1039/C1DT10724K

Social activity

Search articles by author

Spotlight

Advertisements