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. |
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| 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] |
| Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
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| Items | – Name: Title Label: Title Group: Ti Data: 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. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Kubas%2C+Adam%22">Kubas, Adam</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22Hartung%2C+Jens%22">Hartung, Jens</searchLink><relatesTo>2</relatesTo><br /><searchLink fieldCode="AR" term="%22Fink%2C+Karin%22">Fink, Karin</searchLink><relatesTo>1</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Dalton+Transactions%3A+An+International+Journal+of+Inorganic+Chemistry%22">Dalton Transactions: An International Journal of Inorganic Chemistry</searchLink>. Nov2011, Vol. 40 Issue 42, p11289-11295. 7p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Cobalt%22">Cobalt</searchLink><br /><searchLink fieldCode="DE" term="%22Density+functionals%22">Density functionals</searchLink><br /><searchLink fieldCode="DE" term="%22Oxidation%22">Oxidation</searchLink><br /><searchLink fieldCode="DE" term="%22Solvents%22">Solvents</searchLink><br /><searchLink fieldCode="DE" term="%22Furans%22">Furans</searchLink><br /><searchLink fieldCode="DE" term="%22Electrons%22">Electrons</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: 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] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Dalton Transactions: An International Journal of Inorganic Chemistry is the property of Royal Society of Chemistry and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1039/c1dt10724k Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 7 StartPage: 11289 Subjects: – SubjectFull: Cobalt Type: general – SubjectFull: Density functionals Type: general – SubjectFull: Oxidation Type: general – SubjectFull: Solvents Type: general – SubjectFull: Furans Type: general – SubjectFull: Electrons Type: general Titles: – TitleFull: 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. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Kubas, Adam – PersonEntity: Name: NameFull: Hartung, Jens – PersonEntity: Name: NameFull: Fink, Karin IsPartOfRelationships: – BibEntity: Dates: – D: 14 M: 11 Text: Nov2011 Type: published Y: 2011 Identifiers: – Type: issn-print Value: 14779226 Numbering: – Type: volume Value: 40 – Type: issue Value: 42 Titles: – TitleFull: Dalton Transactions: An International Journal of Inorganic Chemistry Type: main |
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