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dc.contributor.authorFarràs, Pau
dc.contributor.authorTeixidor, Francesc
dc.contributor.authorRojo, Isabel
dc.contributor.authorKivekäs, Raikko
dc.contributor.authorSillanpää, Reijo
dc.contributor.authorGonzález-Cardoso, Paul V.
dc.contributor.authorViñas, Clara
dc.date.accessioned2016-08-15T10:46:33Z
dc.date.available2016-08-15T10:46:33Z
dc.date.issued2011-09-09
dc.identifier.citationFarràs, Pau, Teixidor, Francesc, Rojo, Isabel, Kivekäs, Raikko, Sillanpää, Reijo, González-Cardoso, Patricia, & Viñas, Clara. (2011). Relaxed but Highly Compact Diansa Metallacyclophanes. Journal of the American Chemical Society, 133(41), 16537-16552. doi: 10.1021/ja205850pen_IE
dc.identifier.issn1520-5126
dc.identifier.urihttp://hdl.handle.net/10379/5970
dc.description.abstractA series of monoansa [μ-1,1′-PR-3,3′-Co(1,2-C2B9H10)2]− and diansa [8,8′-μ-(1″,2″-benzene)-μ-1,1′-PR-3,3′-Co(1,2-C2B9H9)2]− (R = Ph, tBu) cobaltabisdicarbollidephanes have been synthesized, characterized and studied by NMR, MALDI-TOF-MS, UV-visible spectroscopy, cyclic voltammetry, and DFT calculations. Single crystal X-ray diffraction revealed a highly relaxed structure characterized by the title angle α of 3.8° ([7]−), this being the smallest angle α for a metallacyclophane. In such compounds, the metal-to-phosphorus distance is less than the sum of their van der Waals radii. The availability of a phosphorus lone pair causes an electron delocalization through the metal, as shown by the abnormal 31P NMR chemical shift. Remarkably, the combination of a phosphine donor and a phenyl acceptor moieties causes a synergistic effect that is observed through the different techniques used in this study. The importance of having an available lone pair is demonstrated by the oxidation of phosphorus with hydrogen peroxide, sulfur, and elemental black selenium to produce the corresponding PV compounds. When the electron lone pair is used to form the bond with the corresponding chalcogen atom, the communication between the donor and acceptor moieties on the diansa metallacyclophane is shut down.en_IE
dc.description.sponsorshipSpanish Ministerio de Ciencia e Innovacion (CTQ2010-16237), CSIC (I3P grant to P.F.) and the Generalitat de Catalunya 2009/SGR/00279.en_IE
dc.formatapplication/pdfen_IE
dc.language.isoenen_IE
dc.publisherAmerican Chemical Societyen_IE
dc.relation.ispartofJournal Of The American Chemical Societyen
dc.subjectChemistryen_IE
dc.subjectMetallacarboranesen_IE
dc.subjectMetallocenophanesen_IE
dc.subjectMonoansaen_IE
dc.subjectDiansaen_IE
dc.subjectPhosphanesen_IE
dc.subjectElectron-transferen_IE
dc.titleRelaxed but highly compact diansa metallacyclophanesen_IE
dc.typeArticleen_IE
dc.date.updated2016-08-10T16:58:11Z
dc.identifier.doi10.1021/ja205850p
dc.local.publishedsourcehttp:/dx.doi.org/10.1021/ja205850pen_IE
dc.description.peer-reviewedpeer-reviewed
dc.contributor.funder|~|
dc.internal.rssid9451797
dc.local.contactPau Farras. Email: pau.farrascosta@nuigalway.ie
dc.local.copyrightcheckedNo
dc.local.versionPUBLISHED
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