Please use this identifier to cite or link to this item: http://hdl.handle.net/20.500.12779/5989
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dc.contributor.authorCollini, D.en_us
dc.contributor.authorFabrizi De Biani, Fabriziaen_us
dc.contributor.authorDolzhnikov, D. S.en_us
dc.contributor.authorFemoni, C.en_us
dc.contributor.authorIapalucci, M. C.en_us
dc.contributor.authorLongoni, G.en_us
dc.contributor.authorTiozzo, C.en_us
dc.contributor.authorZacchini, S.en_us
dc.contributor.authorZanello, Pieroen_us
dc.date.accessioned2021-03-30T15:56:39Z-
dc.date.available2021-03-30T15:56:39Z-
dc.date.issued2011-
dc.identifier.issn0020-1669en_US
dc.identifier.urihttp://hdl.handle.net/20.500.12779/5989-
dc.description57016en_US
dc.description.abstractThe previously ill-characterized [HxRh22(CO)(35)](4-/5-) carbonyl cluster has been obtained as a byproduct of the synthesis of [H3Rh13(CO)(24)](2-) and effectively separated by metathesis of their sodium salts with [NEt4]Cl. Although the yields are modest and never exceed 10-15% (based on Rh), this procedure affords spectroscopically pure [H3Rh22(CO)(35)](5-) anion. Formation of the latter in mixture with other Rh clusters was also observed by electrospray ionization-mass spectrometry (EST-MS) in the oxidation of [H2Rh13-(CO)(24)](3-) with Cu2+ salts. The recovery of further amounts of [H3Rh22(CO)(35)](5-) was hampered by too similar solubility of the salts composing the mixture. Conversely, the reaction in CH3CN of [H2Rh13(CO)(24)](3-) with [Cu(MeCN)(4)](+)[BF4](-) leads to the [H2Rh13(CO)(24){Cu(MeCN)}(2)](-) bimetallic cluster. The X-ray crystal structures of [H4Rh22(CO)(35)](4-), [H3Rh22(CO)(35)](5-), and [H2Rh13(CO)(24){Cu(MeCN)}(2)](-) are reported. From a formal point of view, the metal frame of the former two species can be derived by interpenetration along two orthogonal axes of two moieties displaying the structure of the latter. The availability of [H8-nRh22(CO)(35)](n-) salts prompted their detailed chemical, spectroscopic, and electrochemical characterization. The presence of hydride atoms has been directly proved both by ESI-MS and H-1 NMR Moreover, both [H4Rh22(CO)(35)](4-) and [H3Rh22(CO)(35)](5-) undergo distinctive electrochemically reversible redox changes. This allows to assess electrochemical studies as indisputable though circumstantial evidence of the presence of H-1 NMR-silent hydride atoms in isostructural anions of different charge.en_US
dc.language.isoenen_US
dc.relationNoneen_US
dc.relation.ispartofINORGANIC CHEMISTRYen_US
dc.titleSynthesis, structure, and spectroscopic characterization of Rh22 Rh13Cu(MeCN) clusters: assessment of CV and DPV as techniques to circumstantiate the presence of elusive hydride atomsen_US
dc.typeArticleen_US
dc.identifier.doi10.1021/ic101872zen_US
dc.identifier.scopus2-s2.0-79953207040en_US
dc.identifier.isiWOS:000288730400018en_US
dc.relation.volume50en_US
dc.description.firstpage2790en_US
dc.description.lastpage2798en_US
dc.description.thirdmissionNot applicableen_US
item.cerifentitytypePublications-
item.grantfulltextnone-
item.languageiso639-1en-
item.openairecristypehttp://purl.org/coar/resource_type/c_18cf-
item.openairetypeArticle-
item.fulltextNo Fulltext-
crisitem.author.orcid0000-0002-1698-5858-
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