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How molecular oxygen binds to bis[trifluoroacetylacetonato(−1)]cobalt(ii) – ab initioand density functional theory studiesElectronic supplementary information (ESI) available. See DOI: 10.1039/c1dt10724k.

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Title: How molecular oxygen binds to bis[trifluoroacetylacetonato(−1)]cobalt(ii) – ab initioand density functional theory studiesElectronic supplementary information (ESI) available. See DOI: 10.1039/c1dt10724k.
Authors: Kubas, Adam1, Hartung, Jens2, Fink, Karin1
Source: Dalton Transactions: An International Journal of Inorganic Chemistry. Nov2011, Vol. 40 Issue 42, p11289-11295. 7p.
Subjects: Cobalt, Density functionals, Oxidation, Solvents, Furans, Electrons
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)2in 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–O2distance 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 O2π* orbital. [ABSTRACT FROM AUTHOR]
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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)2in 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–O2distance 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 O2π* orbital. [ABSTRACT FROM AUTHOR]
ISSN:14779226
DOI:10.1039/c1dt10724k