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Photoinduced Reductive C−O Couplings from Unsymmetrical Bis-Cyclometalated Pt(IV) Dicarboxylato Complexes

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dc.contributor.authorLópez López, Juan Carlos
dc.contributor.authorBautista, Delia
dc.contributor.authorGonzález Herrero, Pablo
dc.contributor.departmentQuímica Inorgánica
dc.contributor.otherFacultades de la UMU::Facultad de Química
dc.date.accessioned2026-05-26T06:50:18Z
dc.date.available2026-05-26T06:50:18Z
dc.date.copyright© 2024 The Authors
dc.date.issued2024-12-27
dc.description.abstractUnsymmetrical bis-cyclometalated dicarboxylato complexes (OC-6-32)-[Pt(tpy)2(O2CR)2] [tpy = cyclometalated 2-(ptolyl) pyridine, R = t-Bu (1), Me (2), Ph (3), CF3 (4)], are obtained from the reaction of cis-[Pt(tpy)2] with the appropriate PhI(O2CR)2 reagent. Treatment of complexes of this type with different carboxylates (R’CO2 −) results in the formation of mixed-carboxylato derivatives, namely (OC-6-43)-[Pt(tpy)2(O2CMe)(O2CR′)] [R′ = t- Bu (5), CF3 (6), Ph (7)], (OC-6-34)-[Pt(tpy)2(O2CCF3)(O2CR′)] [R′ = t-Bu (8), Me (9), Ph (10)], and (OC-6-34)-[Pt(tpy)2(O2C-t- Bu)(O2CMe)] (11). Irradiation of 1−3 and 5−11 with UV light (365 nm) in MeCN gives 5-methyl-2-(2-pyridyl)phenyl pivalate (12), 5-methyl-2-(2-pyridyl)phenyl acetate (13) or 5-methyl-2-(2- pyridyl)phenyl benzoate (14) as the major photoproduct from most complexes, resulting from a reductive C−O coupling between a tpy ligand and a carboxylato ligand. Cyclometalation of 12−14 at the ensuing Pt(II) species to produce cis-[Pt(tpy)(tpyO2CR/R′)], reduction to cis-[Pt(tpy)2] and isomerization to (OC-6-33)- [Pt(tpy)2(O2CR/R′)2] are identified as secondary processes in most cases. In contrast, complex 4 exclusively photoisomerizes to (OC-6-33)-[Pt(tpy)2(O2CCF3)2] (4′). The C−O couplings are favored for the most electron-rich carboxylato ligands and occur predominantly from the carboxylato trans to N. Consistent with this, a computational study reveals that the lowest singlet and triplet LMCT excited states result from electronic transitions to a dσ* orbital distributed along the N−Pt−O axis, which would trigger the observed processes.
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dc.identifier.citationInorg. Chem. 2025, 64, 662−673
dc.identifier.doihttps://doi.org/10.1021/acs.inorgchem.4c03667
dc.identifier.urihttp://hdl.handle.net/10201/234721
dc.languageeng
dc.publisherAmerican Chemical Society
dc.relationProyectos de Generacion de Conocimiento 2021, Ministerio de Ciencia e Innovación, Agencia Estatal de Investigación, FEDER PID2021-122966NBI00
dc.relation.publisherversionhttps://pubs.acs.org/doi/10.1021/acs.inorgchem.4c03667?ref=PDF
dc.relation.requireshttp://hdl.handle.net/10201/234741
dc.rightsAttribution 4.0 International*
dc.rights.accessRightsinfo:eu-repo/semantics/openAccess
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/*
dc.subject.odsNo relacionado con ningún objetivo de desarrollo sostenible
dc.titlePhotoinduced Reductive C−O Couplings from Unsymmetrical Bis-Cyclometalated Pt(IV) Dicarboxylato Complexes
dc.typeinfo:eu-repo/semantics/article
dc.type.versioninfo:eu-repo/semantics/publishedVersion
dspace.entity.typePublicationes
relation.isAuthorOfPublication940323e4-526b-4ee9-b4f9-728b2b9a5da7
relation.isAuthorOfPublication.latestForDiscovery940323e4-526b-4ee9-b4f9-728b2b9a5da7
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