75610 20190709135531.0 doi 10.1039/c7dt01924f sideral 102672 ART-2017-102672 eng (orcid)0000-0003-1473-0277 Mena, I. Reactivity of the parent amido complexes of iridium with olefins: C-NH2 bond formation versus C-H activation 2017 Access copy available to the general public Unrestricted Herein we report on the different chemical reactivity displayed by two mononuclear terminal amido compounds depending on the nature of the coordinated diene. Hence, treatment of amido-bridged iridium complexes [{Ir(µ-NH2)(tfbb)}3] (1; tfbb = tetrafluorobenzobarrelene) with dppp (dppp = bis(diphenylphosphane)propane) leads to the rupture of the amido bridges forming the mononuclear terminal amido compound [Ir(NH2)(dppp)(tfbb)] (3) in the first stage. On changing the reaction conditions, the formation of a C–NH2 bond between the amido moiety and the coordinated diene is observed and a new dinuclear complex [{Ir(1,2-¿2-4-¿-C12H8F4N)(dppp)}2(µ-dppp)] (4) has been isolated. On the contrary, the diiridium amido-bridged complex [{Ir(µ-NH2)(cod)}2] (2; cod = 1,5-cyclooctadiene) in the presence of dppb (dppb = bis(diphenylphosphane)butane) allows the isolation of a mononuclear complex [Ir(1,2,3-¿3-6-¿-C8H10)H(dppb)] (5), as a consequence of the extrusion of ammonia. The monitoring of the reaction of 2 with dppb (and dppp) allowed us to detect terminal amido complexes [Ir(NH2)(P–P)(cod)] (P–P = dppb (6), dppp (7)) in solution, as confirmed by an X-ray analysis of 7. Complex 7 was observed to evolve into hydrido species 5 at room temperature. DFT studies showed that C–H bond activation occurs through the deprotonation of one methylene fragment of the cod ligand by the highly basic terminal amido moiety instead of C–H oxidative addition to the Ir(I) center. info:eu-repo/grantAgreement/ES/DGA/E07 info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67366-P info:eu-repo/grantAgreement/ES/UZ/KFUPM info:eu-repo/semantics/openAccess All rights reserved http://www.europeana.eu/rights/rr-f/ 4.099 2017 CHEMISTRY, INORGANIC & NUCLEAR 6 / 45 = 0.133 2017 Q1 T1 1.306 2017 Inorganic Chemistry 2017 Q1 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion (orcid)0000-0002-7063-1292 García-Orduña, P. Universidad de Zaragoza (orcid)0000-0001-5823-7965 Polo, V. Universidad de Zaragoza (orcid)0000-0001-8054-2237 Lahoz, F.J. Universidad de Zaragoza (orcid)0000-0003-1707-3022 Casado, M.A. Universidad de Zaragoza (orcid)0000-0001-7154-7239 Oro, L.A. Universidad de Zaragoza 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 46, 34 (2017), 11459-11468 Dalton Trans. Dalton Transactions 1477-9226 615844 http://zaguan.unizar.es/record/75610/files/texto_completo.pdf Postprint 105134 http://zaguan.unizar.es/record/75610/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:75610 articulos driver 2019-07-09-12:02:18 ARTICLE