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Cyclopentadienyl vs indenyl control of thermal/photoactivated CO release in cationic molybdenum(II) dicarbonyl-ethylenediamine complexes

2026-07Artigo científico Acesso aberto
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datacite.subject.fosEngenharia e Tecnologia::Engenharia Química
datacite.subject.fosEngenharia e Tecnologia::Engenharia dos Materiais
dc.contributor.authorBruno, Sofia M.
dc.contributor.authorCalhau, Isabel B.
dc.contributor.authorDias, Tiago M.
dc.contributor.authorSantos, Adriana
dc.contributor.authorSilva, Luis Cunha
dc.contributor.authorNolasco, Mariela M.
dc.contributor.authorGoncalves, Isabel S.
dc.contributor.authorPillinger, Martyn
dc.date.accessioned2026-08-14T11:11:49Z
dc.date.available2026-08-14T11:11:49Z
dc.date.issued2026-07
dc.description.abstractABSTRACT: Molybdenum half-sandwich carbonyl complexes continue to attract attention as potential anticancer agents and prodrugs for therapeutic use of carbon monoxide. Building on the known bioactivity and hydrolytic stability of cyclopentadienyl-based Mo fragments, we report the synthesis, structural characterization, and solution behavior of two cationic half-sandwich complexes, [(eta 5-Cp)Mo(CO)2(en)][BF4] (3) and [(eta 5-Ind)Mo(CO)2(en)][BF4] (4) (Cp = cyclopentadienyl, Ind = indenyl, en = ethylenediamine). Complex 3 is described here for the first time, while 4 was structurally characterized by single-crystal X-ray diffraction, revealing a distorted square-pyramidal geometry with cis-CO ligands and a chelating en ligand positioned beneath the indenyl ring. Both compounds are air-stable in the solid state and exhibit enhanced solubility in polar media due to their ionic nature. UV-vis stability studies under simulated physiological conditions (PBS, pH 7.4, 37 degrees C) show gradual decomposition of both complexes, accelerated by visible-light irradiation and/or the presence of air. CO-release behavior was quantified using the myoglobin assay: the allyl precursors [(eta 5-Cp')Mo(eta 3-C3H5)(CO)2] were inert, whereas complexes 3 and 4 released CO slowly, with 4 exhibiting significantly faster thermal CO liberation (t1/2 approximate to 129 min; 0.74 equiv. CO after 6 h). Complex 3 showed minimal thermal CO release but underwent enhanced and sustained photodecarbonylation under visible-light irradiation, enabling controlled CO delivery. These results identify 3 and 4 as rare examples of Mo-based CO-releasing molecules capable of slow, tunable CO release under biologically relevant conditions, with 3 displaying light-responsive behavior and 4 functioning as a spontaneous thermal CO donor.eng
dc.identifier.citationBruno, S., Calhau, I., Dias, T., Santos, A., Cunha-Silva, L., Nolasco, M., Goncalves, I., & Pillinger, M. (2026). Cyclopentadienyl vs indenyl control of thermal/photoactivated CO release in cationic molybdenum(II) dicarbonyl-ethylenediamine complexes. In: Inorganica Chimica Acta, 2026, vol. 602, article 123348. https://doi.org/10.1016/j.ica.2026.123348
dc.identifier.doi10.1016/j.ica.2026.123348
dc.identifier.issn0020-1693
dc.identifier.urihttp://hdl.handle.net/10400.9/6416
dc.language.isoeng
dc.peerreviewedyes
dc.publisherElsevier
dc.relationCICECO-Aveiro Institute of Materials
dc.relationAssociated Laboratory for Green Chemistry - Clean Technologies and Processes
dc.relationAdvanced materials for carbon dioxide removal from post-combustion streams: sustainable synergistic membranes
dc.relationSupramolecular nanocarriers for the storage and delivery of the gasotransmitter carbon monoxide
dc.relation.hasversionhttps://www.sciencedirect.com/science/article/pii/S0020169326002884?pes=vor&utm_source=clarivate&getft_integrator=clarivate
dc.rights.urihttp://creativecommons.org/licenses/by/4.0/
dc.subjectMolybdenum (Mo)
dc.subjectCrystal structure
dc.subjectCarbon monoxide
dc.subjectOrganometallic chemistry
dc.subjectIndenyl
dc.subjectCyclopentadienyl
dc.titleCyclopentadienyl vs indenyl control of thermal/photoactivated CO release in cationic molybdenum(II) dicarbonyl-ethylenediamine complexeseng
dc.typejournal article
dspace.entity.typePublication
oaire.awardNumberUID/CTM/50011/2019
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oaire.awardNumber2024.17214.PEX
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oaire.awardTitleCICECO-Aveiro Institute of Materials
oaire.awardTitleAssociated Laboratory for Green Chemistry - Clean Technologies and Processes
oaire.awardTitleAdvanced materials for carbon dioxide removal from post-combustion streams: sustainable synergistic membranes
oaire.awardTitleSupramolecular nanocarriers for the storage and delivery of the gasotransmitter carbon monoxide
oaire.awardURIinfo:eu-repo/grantAgreement/FCT/6817 - DCRRNI ID/UID%2FCTM%2F50011%2F2019/PT
oaire.awardURIhttp://hdl.handle.net/10400.9/6093
oaire.awardURIhttp://hdl.handle.net/10400.9/6414
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oaire.citation.titleInorganica Chimica Acta
oaire.citation.volume602
oaire.fundingStream6817 - DCRRNI ID
oaire.fundingStreamConcurso para Atribuição do Estatuto e Financiamento de Laboratórios Associados (LA)
oaire.fundingStreamConcurso para Projetos de Investigação de caráter Exploratório em Todos os Domínios Científicos 2024
oaire.versionhttp://purl.org/coar/version/c_970fb48d4fbd8a85
project.funder.identifierhttp://doi.org/10.13039/501100001871
project.funder.nameFundação para a Ciência e a Tecnologia
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