000075610 001__ 75610
000075610 005__ 20190709135531.0
000075610 0247_ $$2doi$$a10.1039/c7dt01924f
000075610 0248_ $$2sideral$$a102672
000075610 037__ $$aART-2017-102672
000075610 041__ $$aeng
000075610 100__ $$0(orcid)0000-0003-1473-0277$$aMena, I.
000075610 245__ $$aReactivity of the parent amido complexes of iridium with olefins: C-NH2 bond formation versus C-H activation
000075610 260__ $$c2017
000075610 5060_ $$aAccess copy available to the general public$$fUnrestricted
000075610 5203_ $$aHerein we report on the different chemical reactivity displayed by two mononuclear terminal amido compounds depending on the nature of the coordinated diene. Hence, treatment of amido-bridged iridium complexes [{Ir(µ-NH2)(tfbb)}3] (1; tfbb = tetrafluorobenzobarrelene) with dppp (dppp = bis(diphenylphosphane)propane) leads to the rupture of the amido bridges forming the mononuclear terminal amido compound [Ir(NH2)(dppp)(tfbb)] (3) in the first stage. On changing the reaction conditions, the formation of a C–NH2 bond between the amido moiety and the coordinated diene is observed and a new dinuclear complex [{Ir(1,2-¿2-4-¿-C12H8F4N)(dppp)}2(µ-dppp)] (4) has been isolated. On the contrary, the diiridium amido-bridged complex [{Ir(µ-NH2)(cod)}2] (2; cod = 1,5-cyclooctadiene) in the presence of dppb (dppb = bis(diphenylphosphane)butane) allows the isolation of a mononuclear complex [Ir(1,2,3-¿3-6-¿-C8H10)H(dppb)] (5), as a consequence of the extrusion of ammonia. The monitoring of the reaction of 2 with dppb (and dppp) allowed us to detect terminal amido complexes [Ir(NH2)(P–P)(cod)] (P–P = dppb (6), dppp (7)) in solution, as confirmed by an X-ray analysis of 7. Complex 7 was observed to evolve into hydrido species 5 at room temperature. DFT studies showed that C–H bond activation occurs through the deprotonation of one methylene fragment of the cod ligand by the highly basic terminal amido moiety instead of C–H oxidative addition to the Ir(I) center.
000075610 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E07$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2015-67366-P$$9info:eu-repo/grantAgreement/ES/UZ/KFUPM
000075610 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000075610 590__ $$a4.099$$b2017
000075610 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b6 / 45 = 0.133$$c2017$$dQ1$$eT1
000075610 592__ $$a1.306$$b2017
000075610 593__ $$aInorganic Chemistry$$c2017$$dQ1
000075610 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000075610 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, P.$$uUniversidad de Zaragoza
000075610 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, V.$$uUniversidad de Zaragoza
000075610 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, F.J.$$uUniversidad de Zaragoza
000075610 700__ $$0(orcid)0000-0003-1707-3022$$aCasado, M.A.$$uUniversidad de Zaragoza
000075610 700__ $$0(orcid)0000-0001-7154-7239$$aOro, L.A.$$uUniversidad de Zaragoza
000075610 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000075610 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000075610 773__ $$g46, 34 (2017), 11459-11468$$pDalton Trans.$$tDalton Transactions$$x1477-9226
000075610 8564_ $$s615844$$uhttps://zaguan.unizar.es/record/75610/files/texto_completo.pdf$$yPostprint
000075610 8564_ $$s105134$$uhttps://zaguan.unizar.es/record/75610/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000075610 909CO $$ooai:zaguan.unizar.es:75610$$particulos$$pdriver
000075610 951__ $$a2019-07-09-12:02:18
000075610 980__ $$aARTICLE