000106206 001__ 106206
000106206 005__ 20210628121427.0
000106206 0247_ $$2doi$$a10.1021/acs.organomet.9b00409
000106206 0248_ $$2sideral$$a113558
000106206 037__ $$aART-2019-113558
000106206 041__ $$aeng
000106206 100__ $$aCurto, Sheila G.
000106206 245__ $$aC(sp(3))-Cl Bond Activation Promoted by a POP-Pincer Rhodium(I) Complex
000106206 260__ $$c2019
000106206 5060_ $$aAccess copy available to the general public$$fUnrestricted
000106206 5203_ $$aThe complex [RhCl(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (1; xant (PiPr(2))(2) = 9, 9-dimethyl-4, 5-bis-(diisopropylphosphino)xanthene) activates C(sp(3))-Cl bonds of mono- and dichloroalkanes and catalyzes the dehalogenation of chloroalkanes and the homocoupling of benzyl chloride. Complex 1 reacts with chlorocyclohexane to give [RhHCl2(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (2) and cyclohexene and promotes the dehalogenation of the chlorocycloalkane to cyclohexane using 2-propanol solutions of sodium formate as the reducing agent. The oxidative addition of benzyl chloride to 1 leads to [Rh(CH2Ph)Cl-2(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (4). The dehalogenation of this chloroalkane with 2-propanol solutions of sodium formate, in the presence of 1, gives toluene and 1, 2-diphenylethane. The latter is selectively formed with KOH instead of sodium formate. Complex 1 also reacts with trans-1, 2-dichlorocyclohexane and dichloromethane. The reaction with the former gives [RhCl3(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (5) and cyclohexene, whereas complex 1 undergoes oxidative addition of dichloromethane to afford cis-dichloride-[Rh(CH2Cl)-Cl-2(kappa P-3, O, P-{xant((PPr2)-Pr-i)(2)})] (6a), which evolves into its trans-dichloride isomer 6b. The kinetic study of the overall process suggests that the oxidative addition is cis-concerted and the isomerization an intramolecular reaction which takes place through a sigma-C-Cl intermediate with two conformations.
000106206 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E06-17R$$9info:eu-repo/grantAgreement/ES/DGA/LMP148-18$$9info:eu-repo/grantAgreement/ES/MECD/FPU17-04813$$9info:eu-repo/grantAgreement/ES/MINECO-AEI-FEDER/CTQ2017-82935-P
000106206 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000106206 590__ $$a3.804$$b2019
000106206 591__ $$aCHEMISTRY, ORGANIC$$b12 / 57 = 0.211$$c2019$$dQ1$$eT1
000106206 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b6 / 45 = 0.133$$c2019$$dQ1$$eT1
000106206 592__ $$a1.345$$b2019
000106206 593__ $$aInorganic Chemistry$$c2019$$dQ1
000106206 593__ $$aPhysical and Theoretical Chemistry$$c2019$$dQ1
000106206 593__ $$aOrganic Chemistry$$c2019$$dQ1
000106206 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000106206 700__ $$0(orcid)0000-0001-9491-7167$$aHeras, Laura A. de las
000106206 700__ $$0(orcid)0000-0002-4829-7590$$aEsteruelas, Miguel A.
000106206 700__ $$0(orcid)0000-0003-0381-0917$$aOlivan, Montserrat
000106206 700__ $$0(orcid)0000-0003-2094-719X$$aOñate, Enrique
000106206 773__ $$g38, 15 (2019), 3074-3083$$pOrganometallics$$tOrganometallics$$x0276-7333
000106206 8564_ $$s618589$$uhttps://zaguan.unizar.es/record/106206/files/texto_completo.pdf$$yPostprint
000106206 8564_ $$s2834728$$uhttps://zaguan.unizar.es/record/106206/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000106206 909CO $$ooai:zaguan.unizar.es:106206$$particulos$$pdriver
000106206 951__ $$a2021-06-28-09:33:03
000106206 980__ $$aARTICLE