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dc.contributor.authorBaron, Marco
dc.contributor.authorTubaro, Cristina
dc.contributor.authorBasato, Marino
dc.contributor.authorIsse, Abdirisak Ahmed
dc.contributor.authorGennaro, Armando
dc.contributor.authorCavallo, Luigi
dc.contributor.authorGraiff, Claudia
dc.contributor.authorDolmella, Alessandro
dc.contributor.authorFalivene, Laura
dc.contributor.authorCaporaso, Lucia
dc.date.accessioned2016-11-03T13:22:37Z
dc.date.available2016-11-03T13:22:37Z
dc.date.issued2016-06-14
dc.identifier.citationBaron M, Tubaro C, Basato M, Isse AA, Gennaro A, et al. (2016) Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes. Chem Eur J 22: 10211–10224. Available: http://dx.doi.org/10.1002/chem.201600654.
dc.identifier.issn0947-6539
dc.identifier.pmid27297191
dc.identifier.doi10.1002/chem.201600654
dc.identifier.urihttp://hdl.handle.net/10754/621680
dc.description.abstractGold(I) dicarbene complexes [Au2(MeIm-Y-ImMe)2](PF6)2(Y=CH2(1), (CH2)2(2), (CH2)4(4), MeIm=1-methylimidazol-2-ylidene) react with iodine to give the mixed-valence complex [Au(MeIm-CH2-ImMe)2AuI2](PF6)2(1 aI) and the gold(III) complexes [Au2I4(MeIm-Y-ImMe)2](PF6)2(2 cIand 4 cI). Reaction of complexes 1 and 2 with an excess of ICl allows the isolation of the tetrachloro gold(III) complexes [Au2Cl4(MeIm-CH2-ImMe)2](PF6)2(1 cCl) and [Au2Cl4(MeIm-(CH2)2-ImMe)2](Cl)2(2 cCl-Cl) (as main product); remarkably in the case of complex 2, the X-ray molecular structure of the crystals also shows the presence of I-Au-Cl mixed-sphere coordination. The same type of coordination has been observed in the main product of the reaction of complexes 3 or 4 with ICl. The study of the reactivity towards the oxidative addition of halogens to a large series of dinuclear bis(dicarbene) gold(I) complexes has been extended and reviewed. The complexes react with Cl2, Br2and I2to give the successive formation of the mixed-valence gold(I)/gold(III) n aXand gold(III) n cX(excluding compound 1 cI) complexes. However, complex 3 affords with Cl2and Br2the gold(II) complex 3 bX[Au2X2(MeIm-(CH2)3-ImMe)2](PF6)2(X=Cl, Br), which is the predominant species over compound 3 cXeven in the presence of free halogen. The observed different relative stabilities of the oxidised complexes of compounds 1 and 3 have also been confirmed by DFT calculations. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
dc.description.sponsorshipThe University of Padova is gratefully acknowledged for financial support (CPDA20140431 and Assegno di Ricerca Junior CPDR135205).
dc.publisherWiley
dc.subjectDinuclear complexes
dc.titleInsights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes
dc.typeArticle
dc.contributor.departmentChemical Science Program
dc.contributor.departmentKAUST Catalysis Center (KCC)
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Division
dc.identifier.journalChemistry - A European Journal
dc.contributor.institutionDipartimento di Scienze Chimiche; Università degli Studi di Padova; via F. Marzolo 1 35131 Padova Italy
dc.contributor.institutionDipartimento di Chimica; Università di Parma; Viale delle Scienze 17A 43100 Parma Italy
dc.contributor.institutionDipartimento di Scienze del Farmaco; Università degli Studi di Padova; via F. Marzolo 5 35131 Padova Italy
dc.contributor.institutionDipartimento di Chimica e Biologia; Università di Salerno; Via Papa Giovanni Paolo II 84084 Fisciano Italy
kaust.personCavallo, Luigi
kaust.personFalivene, Laura
dc.relation.isSupplementedByBaron, M., Tubaro, C., Basato, M., Isse, A. A., Gennaro, A., Cavallo, L., … Caporaso, L. (2016). CCDC 1407688: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j7t9w
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j7t9w
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624505
dc.relation.isSupplementedByBaron, M., Tubaro, C., Basato, M., Isse, A. A., Gennaro, A., Cavallo, L., … Caporaso, L. (2016). CCDC 1408064: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j86ff
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j86ff
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624507
dc.relation.isSupplementedByBaron, M., Tubaro, C., Basato, M., Isse, A. A., Gennaro, A., Cavallo, L., … Caporaso, L. (2016). CCDC 1448761: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1kmk7z
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1kmk7z
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624558
dc.relation.isSupplementedByBaron, M., Tubaro, C., Basato, M., Isse, A. A., Gennaro, A., Cavallo, L., … Caporaso, L. (2016). CCDC 1407689: Experimental Crystal Structure Determination [Data set]. Cambridge Crystallographic Data Centre. https://doi.org/10.5517/ccdc.csd.cc1j7tbx
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j7tbx
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624506
dc.date.published-online2016-06-14
dc.date.published-print2016-07-11


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