131449 20240209155915.0 doi 10.1021/acscatal.1c00602 sideral 126887 ART-2021-126887 eng Galiana-Cameo M. Universidad de Zaragoza (orcid)0000-0002-2043-4864 Metal-Ligand Cooperative Proton Transfer as an Efficient Trigger for Rhodium-NHC-Pyridonato Catalyzed gem-Specific Alkyne Dimerization 2021 The 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. Access copy available to the general public Unrestricted info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R info:eu-repo/grantAgreement/ES/MECD/FPU17-05417 info:eu-repo/grantAgreement/ES/MICINN-FEDER/PID2019-103965GB-I00 info:eu-repo/grantAgreement/ES/MICINN/PGC2018-099383-B-I00 info:eu-repo/grantAgreement/ES/MINECO/IJCI-2015-27029 info:eu-repo/semantics/openAccess by http://creativecommons.org/licenses/by/3.0/es/ 13.7 2021 CHEMISTRY, PHYSICAL 19 / 165 = 0.115 2021 Q1 T1 4.202 2021 Chemistry (miscellaneous) 2021 Q1 Catalysis 2021 Q1 20.8 2021 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion Urriolabeitia A. Universidad de Zaragoza (orcid)0000-0001-9352-6922 Barrenas E. Passarelli V. Universidad de Zaragoza (orcid)0000-0002-1735-6439 Pérez-Torrente J.J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Di Giuseppe A. (orcid)0000-0002-3666-5800 Polo V. Universidad de Zaragoza (orcid)0000-0001-5823-7965 Castarlenas R. (orcid)0000-0003-4460-8678 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 11, 12 (2021), 7553-7567 ACS catal. ACS CATALYSIS 2155-5435 4154250 http://zaguan.unizar.es/record/131449/files/texto_completo.pdf Versión publicada 3140454 http://zaguan.unizar.es/record/131449/files/texto_completo.jpg?subformat=icon icon Versión publicada oai:zaguan.unizar.es:131449 articulos driver 2024-02-09-14:29:30 ARTICLE