Dancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2

Handle URI:
http://hdl.handle.net/10754/562619
Title:
Dancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2
Authors:
Poater, Albert; Cavallo, Luigi ( 0000-0002-1398-338X )
Abstract:
The present study pretends to assign the correct multiplicity state to dinuclear copper complexes when interacting with free molecular oxygen. Recently, the formation of a bridge butterfly μ-η2: η2-peroxo dicopper core structure stabilized by the direct interaction of the counterion, a carboxylate group that allows the double bridge linking both metal-centre atoms, was characterized by crystallography. This system was assigned as a diradical singlet with Ms = 0. However, after new calculations it has turned out to be triplet (Ms = 1) despite the stabilization for this latter multiplicity state is not high. Here, the factors that contribute to make this structure display a multiplicity different with respect to the previously expected diradical singlet are described. In the present theoretical study, the roles of the αSp ligand constraints and the counterion are unravelled. On the other hand, the relative stability between the butterfly μ-η2: η2-peroxo structure and the isomeric bis(μ-oxo) species is also on discussion. Despite the relative stabilities of all these either structural or electronic isomeric species are supposed to depend on the computational method, which is a difficulty to reach a definite conclusion about the nature of the active species, all DFT methods using either pure or not pure DFT functionals here reach the same conclusion, favoring the triplet as the ground state for the butterfly μ-η2: η2-peroxo dicopper core structure, and the bis(μ-oxo) species when removing the benzoate counterion. © Springer-Verlag Berlin Heidelberg 2013.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division; Chemical Science Program
Publisher:
Springer Verlag
Journal:
Theoretical Chemistry Accounts
Issue Date:
29-Jan-2013
DOI:
10.1007/s00214-013-1336-x
Type:
Article
ISSN:
1432881X
Sponsors:
AP is grateful to the European Commission (CIG09-GA-2011-293900), Spanish MICINN (Ramon y Cajal contract RYC-2009-05226), and Generalitat de Catalunya (2011BE100793). LC thanks ENEA (www.enea.it) and the HPC team for support as for using the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) Portici (Naples, Italy).
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorPoater, Alberten
dc.contributor.authorCavallo, Luigien
dc.date.accessioned2015-08-03T10:58:38Zen
dc.date.available2015-08-03T10:58:38Zen
dc.date.issued2013-01-29en
dc.identifier.issn1432881Xen
dc.identifier.doi10.1007/s00214-013-1336-xen
dc.identifier.urihttp://hdl.handle.net/10754/562619en
dc.description.abstractThe present study pretends to assign the correct multiplicity state to dinuclear copper complexes when interacting with free molecular oxygen. Recently, the formation of a bridge butterfly μ-η2: η2-peroxo dicopper core structure stabilized by the direct interaction of the counterion, a carboxylate group that allows the double bridge linking both metal-centre atoms, was characterized by crystallography. This system was assigned as a diradical singlet with Ms = 0. However, after new calculations it has turned out to be triplet (Ms = 1) despite the stabilization for this latter multiplicity state is not high. Here, the factors that contribute to make this structure display a multiplicity different with respect to the previously expected diradical singlet are described. In the present theoretical study, the roles of the αSp ligand constraints and the counterion are unravelled. On the other hand, the relative stability between the butterfly μ-η2: η2-peroxo structure and the isomeric bis(μ-oxo) species is also on discussion. Despite the relative stabilities of all these either structural or electronic isomeric species are supposed to depend on the computational method, which is a difficulty to reach a definite conclusion about the nature of the active species, all DFT methods using either pure or not pure DFT functionals here reach the same conclusion, favoring the triplet as the ground state for the butterfly μ-η2: η2-peroxo dicopper core structure, and the bis(μ-oxo) species when removing the benzoate counterion. © Springer-Verlag Berlin Heidelberg 2013.en
dc.description.sponsorshipAP is grateful to the European Commission (CIG09-GA-2011-293900), Spanish MICINN (Ramon y Cajal contract RYC-2009-05226), and Generalitat de Catalunya (2011BE100793). LC thanks ENEA (www.enea.it) and the HPC team for support as for using the ENEA-GRID and the HPC facilities CRESCO (www.cresco.enea.it) Portici (Naples, Italy).en
dc.publisherSpringer Verlagen
dc.subjectμ-η2:η2-peroxoen
dc.subjectBenzoate counteranionen
dc.subjectBis(μ-oxo)en
dc.subjectDFT calculationsen
dc.subjectDicopperen
dc.subjectMultiplicityen
dc.titleDancing multiplicity states supported by a carboxylated group in dicopper structures bonded to O2en
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.identifier.journalTheoretical Chemistry Accountsen
dc.contributor.institutionDepartament de Química, Institut de Química Computacional, Universitat de Girona, Campus de Montilivi, 17071 Girona, Catalonia, Spainen
kaust.authorCavallo, Luigien
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