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Hexafluoroacetylacetonate (hfac) as ligand for pentamethylcyclopentadienyl (Cp*) rhodium and iridium complexes: Some surprising results, including an Ir3Na1O4 cubane structure

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dc.contributor.authorDuChane, Christine M.en
dc.contributor.authorMerola, Joseph S.en
dc.date.accessioned2020-11-30T12:56:17Zen
dc.date.available2020-11-30T12:56:17Zen
dc.date.issued2020-12-14en
dc.date.updated2020-11-26T20:30:14Zen
dc.description.abstractAttempts to prepare hexafluoroacetylacetonate (hfac) piano stool complexes of pentamethylcyclopentadienyl Cp∗ iridium and rhodium led to a surprising array of unexpected products. The desired complex, Cp∗M(hfac)Cl, was obtained following the reaction of sodium hexafluoroacetylacetonate (hfacNa) with [Cp ∗MCl 2 ] 2 in dichloromethane. Variations of this synthetic method resulted in twelve unique crystal- lographically identified products, eleven of which contain the hfac ligand or a trifluoroacetylacetonate (TFA) ligand, either coordinated to the metal or as a non-coordinating anion. Five dinuclear Cp ∗iridium hydroxo-bridged products with various fluorinated non-coordinating anions were obtained. The most in- triguing two complexes are trinuclear Cp ∗Ir III hydroxo-bridged clusters that have, at their core, an Ir 3 NaO 4 cubane structure. Attempts to devise rational syntheses of the hydroxo-bridged cluster compounds were not successful. Generation of the TFA moieties likely occurred following degradation of Cp ∗Ir(hfac)Cl. The reaction between [Cp ∗MCl 2 ] 2 and 1,1,1-trifluoroacetylacetonate (tfac) proceeded as expected to give Cp ∗M(tfac)Cl with no observed side product formation, indicating that the metal-coordinated tfac moiety is significantly more stable than the metal-coordinated hfac moiety.en
dc.description.versionPublished versionen
dc.format.extentPages 121552-121562en
dc.format.extent10 page(s)en
dc.format.mimetypeapplication/pdfen
dc.identifier.doihttps://doi.org/10.1016/j.jorganchem.2020.121552en
dc.identifier.orcidMerola, Joseph [0000-0002-1743-1777]en
dc.identifier.urihttp://hdl.handle.net/10919/100968en
dc.identifier.volume929en
dc.language.isoenen
dc.rightsIn Copyright (InC)en
dc.rights.urihttp://rightsstatements.org/vocab/InC/1.0/en
dc.subject0302 Inorganic Chemistryen
dc.subject0305 Organic Chemistryen
dc.subject0399 Other Chemical Sciencesen
dc.subjectOrganic Chemistryen
dc.titleHexafluoroacetylacetonate (hfac) as ligand for pentamethylcyclopentadienyl (Cp*) rhodium and iridium complexes: Some surprising results, including an Ir3Na1O4 cubane structureen
dc.title.serialJournal of Organometallic Chemistryen
dc.typeArticle - Refereeden
dc.type.dcmitypeTexten
dc.type.otherArticleen
dcterms.dateAccepted2020-10-03en
pubs.organisational-group/Virginia Tech/Scienceen
pubs.organisational-group/Virginia Tech/Faculty of Health Sciencesen
pubs.organisational-group/Virginia Tech/All T&R Facultyen
pubs.organisational-group/Virginia Tech/Science/Chemistryen
pubs.organisational-group/Virginia Tech/Science/COS T&R Facultyen
pubs.organisational-group/Virginia Tech/University Research Institutes/Fralin Life Sciences/Durelle Scotten
pubs.organisational-group/Virginia Techen
pubs.organisational-group/Virginia Tech/University Research Institutes/Fralin Life Sciencesen
pubs.organisational-group/Virginia Tech/University Research Institutesen

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