Scrutinizing the Noninnocence of Quinone Ligands in Ruthenium Complexes: Insights from Structural, Electronic, Energy, and Effective Oxidation State Analyses
dc.contributor.author
dc.date.accessioned
2016-09-16T07:12:17Z
dc.date.available
2016-09-16T07:12:17Z
dc.date.issued
2016-02-11
dc.identifier.issn
0020-1669
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dc.description.abstract
The most relevant manifestations of ligand noninnocence of quinone and bipyridine derivatives are thoroughly scrutinized and discussed through an extensive and systematic set of octahedral ruthenium complexes, [(en)2RuL]z, in four oxidation states (z = +3, +2, +1, and 0). The characteristic structural deformation of ligands upon coordination/noninnocence is put into context with the underlying electronic structure of the complexes and its change upon reduction. In addition, by means of decomposing the corresponding reductions into electron transfer and structural relaxation subprocesses, the energetic contribution of these structural deformations to the redox energetics is revealed. The change of molecular electron density upon metal- and ligand-centered reductions is also visualized and shown to provide novel insights into the corresponding redox processes. Moreover, the charge distribution of the π-subspace is straightforwardly examined and used as indicator of ligand noninnocence in the distinct oxidation states of the complexes. The aromatization/dearomatization processes of ligand backbones are also monitored using magnetic (NICS) and electronic (PDI) indicators of aromaticity, and the consequences to noninnocent behavior are discussed. Finally, the recently developed effective oxidation state (EOS) analysis is utilized, on the one hand, to test its applicability for complexes containing noninnocent ligands, and, on the other hand, to provide new insights into the magnitude of state mixings in the investigated complexes. The effect of ligand substitution, nature of donor atom, ligand frame modification on these manifestations, and measures is discussed in an intuitive and pedagogical manner
dc.description.sponsorship
M.G. and P.S. are thankful for financial support from the FEDER grant UNGI10-4E-801 and MINECO grant CTQ2014-59212-P/BQU
dc.format.extent
15 p.
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application/pdf
dc.language.iso
eng
dc.publisher
American Chemical Society (ACS)
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info:eu-repo/grantAgreement/MINECO//CTQ2014-59212-P/ES/SPIN STATE AND ENZYMATIC CATALYSIS BASED ON BOTTOM-UP COMPUTATIONAL DESIGN/
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Reproducció digital del document publicat a: http://dx.doi.org/10.1021/acs.inorgchem.5b02543
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© Inorganic Chemistry, 2016, vol. 55, p. 2185-2199
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Articles publicats (D-Q)
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Tots els drets reservats
dc.source
Skara, G. Gimferrer, M. De Proft, F. Salvador Sedano, Pedro Pinter, B. 2016 Scrutinizing the Noninnocence of Quinone Ligands in Ruthenium Complexes: Insights from Structural, Electronic, Energy, and Effective Oxidation State Analyses Inorganic Chemistry 55 2185 2199
dc.title
Scrutinizing the Noninnocence of Quinone Ligands in Ruthenium Complexes: Insights from Structural, Electronic, Energy, and Effective Oxidation State Analyses
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/embargoedAccess
dc.date.embargoEndDate
info:eu-repo/date/embargoEnd/2026-01-01
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
025665
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dc.relation.ProjectAcronym
dc.identifier.eissn
1520-510X