000084163 001__ 84163
000084163 005__ 20200117213745.0
000084163 0247_ $$2doi$$a10.1021/acs.organomet.8b00500
000084163 0248_ $$2sideral$$a108839
000084163 037__ $$aART-2018-108839
000084163 041__ $$aeng
000084163 100__ $$aBoudreault, P.L.T.
000084163 245__ $$aPyridyl-Directed C-H and C-Br Bond Activations Promoted by Dimer Iridium-Olefin Complexes
000084163 260__ $$c2018
000084163 5060_ $$aAccess copy available to the general public$$fUnrestricted
000084163 5203_ $$aComplexes [Ir(μ-Cl)(η2-C8H14)2]2 (1) and [Ir(μ-Cl)(η4-C8H12)]2 (2) promote the pyridyl-directed ortho-CH and ortho-CBr activations of the phenyl substituent of 2-(2-bromophenyl)pyridine. The formed products depend upon the olefin of the dimer, which governs the kinetic preference of the activation. The cyclooctene complex 1 reacts with the substituted heterocycle to give (η2-C8H14)2Ir(μ-Cl)2Ir{κ2-C,N-[C6BrH3-py]}2 (3), in acetone, at room temperature. Treatment of 3 with K(acac) affords Ir(acac)(η2-C8H14)2 (4) and Ir(acac){κ2-C,N-[C6BrH3-py]}2 (5; acac = acetylacetone). Under more severe conditions, 2-ethoxyethanol under reflux, the reaction of 1 with the heterocycle gives a yellow solid, which yields a 5:82:7 mixture of 5, Ir(acac){κ2-C,N-[C6BrH3-py]}{κ2-C,N-[C6H4-py]} (6), and Ir(acac){κ2-C,N-[C6H4-py]}2 (7) by reaction with K(acac). In acetone or toluene, at room temperature, 2-(2-bromophenyl)pyridine breaks the chloride bridges of dimer 2 to form IrCl(η4-C8H12){κ1-N-[py-C6BrH4]} (8), which evolves into IrClBr{κ2-C,N-[C6H4-py]}(η4-C8H12) (9) as a result of the oxidative addition of the ortho-CBr of the phenyl substituent to the metal center. Treatment of 9 with Ag2O in acetylacetone leads to Ir(acac){κ2-C,N-[C6H4-py]}{κ1-C, η2-[C8H12-(C3-acac)]} (10), as a consequence of the replacement of the halides by an O,O-chelate acac ligand and the outside to metal nucleophilic attack of a second acac group to the diene C–C double bond disposed trans to bromide.
000084163 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-17R$$9info:eu-repo/grantAgreement/ES/DGA/FEDER$$9info:eu-repo/grantAgreement/ES/DGA/FSE$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2016-81797-REDC$$9info:eu-repo/grantAgreement/ES/MINECO/CTQ2017-82935-P
000084163 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000084163 590__ $$a4.1$$b2018
000084163 591__ $$aCHEMISTRY, ORGANIC$$b11 / 57 = 0.193$$c2018$$dQ1$$eT1
000084163 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 45 = 0.111$$c2018$$dQ1$$eT1
000084163 592__ $$a1.473$$b2018
000084163 593__ $$aInorganic Chemistry$$c2018$$dQ1
000084163 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000084163 593__ $$aOrganic Chemistry$$c2018$$dQ1
000084163 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000084163 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, M.A.
000084163 700__ $$aMora, E.$$uUniversidad de Zaragoza
000084163 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, E.
000084163 700__ $$aTsai, J.Y.
000084163 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000084163 773__ $$g37, 21 (2018), 3770–3779$$pOrganometallics$$tOrganometallics$$x0276-7333
000084163 8564_ $$s430058$$uhttps://zaguan.unizar.es/record/84163/files/texto_completo.pdf$$yPostprint
000084163 8564_ $$s60614$$uhttps://zaguan.unizar.es/record/84163/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000084163 909CO $$ooai:zaguan.unizar.es:84163$$particulos$$pdriver
000084163 951__ $$a2020-01-17-21:29:22
000084163 980__ $$aARTICLE