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dc.contributor.authorAlemayehu, Abraham
dc.contributor.authorVazquez Lima, Hugo
dc.contributor.authorGagnon, Kevin J.
dc.contributor.authorGhosh, Abhik
dc.date.accessioned2018-10-12T09:55:06Z
dc.date.available2018-10-12T09:55:06Z
dc.date.issued2017-04-19
dc.description.abstractGiven the many applications of ruthenium porphyrins, the rarity of ruthenium corroles and the underdeveloped state of their chemistry are clearly indicative of an area ripe for significant breakthroughs. The tendency of ruthenium corroles to form unreactive metal–metal-bonded dimers has been recognized as a key impediment in this area. Herein, by exposing free-base meso-tris(p-X-phenyl)corroles, H<sub>3</sub>[TpXPC] (X = CF<sub>3</sub>, H, Me, and OMe), and [Ru(COD)Cl<sub>2</sub>]x in refluxing 2-methoxyethanol to nitrite, we have been able to reliably intercept the series Ru[TpXPC](NO) in a matter of seconds to minutes and subsequently RuVI[TpXPC](N), the products of a second deoxygenation, over some 16 h. Two of the Ru<sup>VI</sup>N complexes and one ruthenium corrole dimer could be crystallographically analyzed; the Ru–N<sub>nitrido</sub> distance was found to be ∼1.61 Å, consistent with the triple-bonded character of the Ru<sup>VI</sup>N units and essentially identical with the Os–N<sub>nitrido</sub> distance in analogous osmium corroles. Spectroscopic and density functional theory (DFT) calculations suggest that the RuNO corroles are best viewed as innocent {RuNO}6 complexes, whereas the analogous FeNO corroles are noninnocent, i.e., best viewed as {FeNO}7-corrole<sup>•2–</sup>. Both RuVIN and Os<sup>VI</sup>N corroles exhibit sharp Soret bands, suggestive of an innocent macrocycle. A key difference between the two metals is that the Soret maxima of the Os<sup>VI</sup>N corroles are red-shifted some 25 nm relative to those of the Ru<sup>VI</sup>N complexes. Careful time-dependent DFT studies indicate that this difference is largely attributable to relativistic effects in Os<sup>VI</sup>N corroles. The availability of two new classes of mononuclear ruthenium corroles potentially opens the door to new applications, in such areas as catalysis and cancer therapy.en_US
dc.description.sponsorshipU.S. Department of Energyen_US
dc.descriptionThis document is the Accepted Manuscript version of a Published Work that appeared in final form in <i>Inorganic Chemistry</i>, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see <a href=https://doi.org/10.1021/acs.inorgchem.7b00377> https://doi.org/10.1021/acs.inorgchem.7b00377</a>.en_US
dc.identifier.citationAlemayehu, A., Vazquez-Lima, H., Gagnon, K.J. & Ghosh, A. (2017). Stepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effects. Inorganic Chemistry. 56(9), 5285-5294. https://doi.org/10.1021/acs.inorgchem.7b00377en_US
dc.identifier.cristinIDFRIDAID 1542969
dc.identifier.doi10.1021/acs.inorgchem.7b00377
dc.identifier.issn0020-1669
dc.identifier.issn1520-510X
dc.identifier.urihttps://hdl.handle.net/10037/13951
dc.language.isoengen_US
dc.publisherAmerican Chemical Societyen_US
dc.relation.journalInorganic Chemistry
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/FRINATEK/231086/Norway/Corroles as a Platform for Fundamental Transition Metal Chemistry, with Emphasis on Heavy Elements//en_US
dc.relation.projectIDinfo:eu-repo/grantAgreement/RCN/NANO2021/262229/Norway/Metallocorroles for photodynamic therapy and bioimaging//en_US
dc.rights.accessRightsopenAccessen_US
dc.subjectVDP::Mathematics and natural science: 400::Chemistry: 440en_US
dc.subjectVDP::Matematikk og Naturvitenskap: 400::Kjemi: 440en_US
dc.titleStepwise Deoxygenation of Nitrite as a Route to Two Families of Ruthenium Corroles: Group 8 Periodic Trends and Relativistic Effectsen_US
dc.typeJournal articleen_US
dc.typeTidsskriftartikkelen_US
dc.typePeer revieweden_US


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