000131449 001__ 131449
000131449 005__ 20240209155915.0
000131449 0247_ $$2doi$$a10.1021/acscatal.1c00602
000131449 0248_ $$2sideral$$a126887
000131449 037__ $$aART-2021-126887
000131449 041__ $$aeng
000131449 100__ $$0(orcid)0000-0002-2043-4864$$aGaliana-Cameo M.$$uUniversidad de Zaragoza
000131449 245__ $$aMetal-Ligand Cooperative Proton Transfer as an Efficient Trigger for Rhodium-NHC-Pyridonato Catalyzed gem-Specific Alkyne Dimerization
000131449 260__ $$c2021
000131449 5060_ $$aAccess copy available to the general public$$fUnrestricted
000131449 5203_ $$aThe mononuclear square-planar Rh{¿2-X, N-(Xpy)}(¿2-coe)(IPr) (X = O, NH, NMe, S) complexes have been synthesized from the dinuclear precursor [Rh(µ-Cl)(IPr)( ¿2-coe)]2 and the corresponding 2-heteroatom-pyridinate salts. The Rh-NHC-pyridinato derivatives are highly efficient catalysts for gem-specific alkyne dimerization. Particularly, the chelating N, O-pyridonato complex displays turnover frequency levels of up 17 000 h-1 at room temperature. Mechanistic investigations and density functional theory calculations suggest a pyridonato-based metal-ligand cooperative proton transfer as responsible for the enhancement of catalytic activity. The initial deprotonation of a Rh-p-alkyne complex by the oxo-functionality of a ¿1-N-pyridonato moiety has been established to be the rate-limiting step, whereas the preferential protonation of the terminal position of a p-coordinated alkyne accounts for the exclusive observation of head-to-tail enynes. The catalytic cycle is closed by a very fast alkenyl-alkynyl reductive elimination. © 2021 American Chemical Society.
000131449 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MECD/FPU17-05417$$9info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00$$9info:eu-repo/grantAgreement/ES/MICINN/PGC2018-099383-B-I00$$9info:eu-repo/grantAgreement/ES/MINECO/IJCI-2015-27029
000131449 540__ $$9info:eu-repo/semantics/openAccess$$aby$$uhttp://creativecommons.org/licenses/by/3.0/es/
000131449 590__ $$a13.7$$b2021
000131449 591__ $$aCHEMISTRY, PHYSICAL$$b19 / 165 = 0.115$$c2021$$dQ1$$eT1
000131449 592__ $$a4.202$$b2021
000131449 593__ $$aChemistry (miscellaneous)$$c2021$$dQ1
000131449 593__ $$aCatalysis$$c2021$$dQ1
000131449 594__ $$a20.8$$b2021
000131449 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion
000131449 700__ $$0(orcid)0000-0001-9352-6922$$aUrriolabeitia A.$$uUniversidad de Zaragoza
000131449 700__ $$aBarrenas E.
000131449 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli V.$$uUniversidad de Zaragoza
000131449 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente J.J.$$uUniversidad de Zaragoza
000131449 700__ $$0(orcid)0000-0002-3666-5800$$aDi Giuseppe A.
000131449 700__ $$0(orcid)0000-0001-5823-7965$$aPolo V.$$uUniversidad de Zaragoza
000131449 700__ $$0(orcid)0000-0003-4460-8678$$aCastarlenas R.
000131449 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000131449 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000131449 773__ $$g11, 12 (2021), 7553-7567$$pACS catal.$$tACS CATALYSIS$$x2155-5435
000131449 8564_ $$s4154250$$uhttps://zaguan.unizar.es/record/131449/files/texto_completo.pdf$$yVersión publicada
000131449 8564_ $$s3140454$$uhttps://zaguan.unizar.es/record/131449/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada
000131449 909CO $$ooai:zaguan.unizar.es:131449$$particulos$$pdriver
000131449 951__ $$a2024-02-09-14:29:30
000131449 980__ $$aARTICLE