Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes

Handle URI:
http://hdl.handle.net/10754/621680
Title:
Insights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexes
Authors:
Baron, Marco; Tubaro, Cristina ( 0000-0001-7724-735X ) ; Basato, Marino; Isse, Abdirisak Ahmed ( 0000-0003-0966-1983 ) ; Gennaro, Armando ( 0000-0002-7665-7178 ) ; Cavallo, Luigi ( 0000-0002-1398-338X ) ; Graiff, Claudia ( 0000-0002-9908-6961 ) ; Dolmella, Alessandro ( 0000-0003-1287-6635 ) ; Falivene, Laura ( 0000-0003-1509-6191 ) ; Caporaso, Lucia ( 0000-0001-6623-3315 )
Abstract:
Gold(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.
KAUST Department:
KAUST Catalysis Center (KCC)
Citation:
Baron 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.
Publisher:
Wiley-Blackwell
Journal:
Chemistry - A European Journal
Issue Date:
14-Jun-2016
DOI:
10.1002/chem.201600654
PubMed ID:
27297191
Type:
Article
ISSN:
0947-6539
Sponsors:
The University of Padova is gratefully acknowledged for financial support (CPDA20140431 and Assegno di Ricerca Junior CPDR135205).
Is Supplemented By:
Baron, 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; DOI:10.5517/ccdc.csd.cc1j7t9w; HANDLE:http://hdl.handle.net/10754/624505; Baron, 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; DOI:10.5517/ccdc.csd.cc1j86ff; HANDLE:http://hdl.handle.net/10754/624507; Baron, 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; DOI:10.5517/ccdc.csd.cc1kmk7z; HANDLE:http://hdl.handle.net/10754/624558; Baron, 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; DOI:10.5517/ccdc.csd.cc1j7tbx; HANDLE:http://hdl.handle.net/10754/624506
Appears in Collections:
Articles; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBaron, Marcoen
dc.contributor.authorTubaro, Cristinaen
dc.contributor.authorBasato, Marinoen
dc.contributor.authorIsse, Abdirisak Ahmeden
dc.contributor.authorGennaro, Armandoen
dc.contributor.authorCavallo, Luigien
dc.contributor.authorGraiff, Claudiaen
dc.contributor.authorDolmella, Alessandroen
dc.contributor.authorFalivene, Lauraen
dc.contributor.authorCaporaso, Luciaen
dc.date.accessioned2016-11-03T13:22:37Z-
dc.date.available2016-11-03T13:22:37Z-
dc.date.issued2016-06-14en
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.en
dc.identifier.issn0947-6539en
dc.identifier.pmid27297191-
dc.identifier.doi10.1002/chem.201600654en
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.en
dc.description.sponsorshipThe University of Padova is gratefully acknowledged for financial support (CPDA20140431 and Assegno di Ricerca Junior CPDR135205).en
dc.publisherWiley-Blackwellen
dc.subjectDinuclear complexesen
dc.titleInsights into the Halogen Oxidative Addition Reaction to Dinuclear Gold(I) Di(NHC) Complexesen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.identifier.journalChemistry - A European Journalen
dc.contributor.institutionDipartimento di Scienze Chimiche; Università degli Studi di Padova; via F. Marzolo 1 35131 Padova Italyen
dc.contributor.institutionDipartimento di Chimica; Università di Parma; Viale delle Scienze 17A 43100 Parma Italyen
dc.contributor.institutionDipartimento di Scienze del Farmaco; Università degli Studi di Padova; via F. Marzolo 5 35131 Padova Italyen
dc.contributor.institutionDipartimento di Chimica e Biologia; Università di Salerno; Via Papa Giovanni Paolo II 84084 Fisciano Italyen
kaust.authorCavallo, Luigien
kaust.authorFalivene, Lauraen
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.cc1j7t9wen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j7t9wen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624505en
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.cc1j86ffen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j86ffen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624507en
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.cc1kmk7zen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1kmk7zen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624558en
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.cc1j7tbxen
dc.relation.isSupplementedByDOI:10.5517/ccdc.csd.cc1j7tbxen
dc.relation.isSupplementedByHANDLE:http://hdl.handle.net/10754/624506en

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