147040 20260217205605.0 doi 10.1021/acs.organomet.4c00409 sideral 140734 ART-2024-140734 eng Español-Sánchez, Belinda Tuning the pyridone scaffold within a Rhodium-NHC platform for gem-specific alkyne dimerization via a ligand-assisted proton shuttle mechanism 2024 Access copy available to the general public Unrestricted A series of mononuclear square-planar Rh{κ2N,O-BHetA}(η2-coe)(NHC) (BHetA = Bis-Heteroatomic Acidato) complexes have been prepared. Modifications of the pyridonato BHetA-type ligand architecture include 4-Me, 5-Me, 6-Me, 3-Br, 4-Br, 4-OMe, and 5-NO2 substitutions as well as pyrimidonato, succinimidato, and 2-piperidonato catalysts. Two structural isomers have been observed for the complexes, depending on the stereoelectronic properties of the ligand. The structure–activity relationship has been studied for gem-specific alkyne dimerization via a cooperative ligand-assisted proton shuttle mechanism. Density functional theory calculations have revealed a mechanistic pathway involving the hemilabile coordination of the BHetA ligand, CMD deprotonation, π-alkyne protonation, and reductive elimination. The increase in oxygen basicity imparted by the substituent in the pyridonato ligand is key, the 4-methyl derivative being the most active catalyst. However, a favored iminol–amide tautomerization precludes an increase in catalytic activity for the more basic saturated piperidonato catalyst. info:eu-repo/grantAgreement/ES/DGA/E42-23R info:eu-repo/grantAgreement/ES/MECD/FPU17-05417 info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033 info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00 info:eu-repo/semantics/openAccess by-nc-nd https://creativecommons.org/licenses/by-nc-nd/4.0/deed.es 2.9 2024 CHEMISTRY, ORGANIC 14 / 57 = 0.246 2024 Q1 T1 CHEMISTRY, INORGANIC & NUCLEAR 17 / 43 = 0.395 2024 Q2 T2 0.676 2024 Inorganic Chemistry 2024 Q2 Physical and Theoretical Chemistry 2024 Q2 Organic Chemistry 2024 Q2 5.1 2024 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion Galiana-Cameo, María Universidad de Zaragoza (orcid)0000-0002-2043-4864 Urriolabeitia, Asier Universidad de Zaragoza (orcid)0000-0001-9352-6922 Polo, Victor Universidad de Zaragoza (orcid)0000-0001-5823-7965 Passarelli, Vincenzo (orcid)0000-0002-1735-6439 Pérez-Torrente, Jesús J. Universidad de Zaragoza (orcid)0000-0002-3327-0918 Castarlenas, Ricardo (orcid)0000-0003-4460-8678 2010 760 Universidad de Zaragoza Dpto. Química Inorgánica Área Química Inorgánica 2013 765 Universidad de Zaragoza Dpto. Química Orgánica Área Química Orgánica 2012 755 Universidad de Zaragoza Dpto. Química Física Área Química Física 43, 22 (2024), 2951-2962 Organometallics Organometallics 0276-7333 1442269 http://zaguan.unizar.es/record/147040/files/texto_completo.pdf Postprint 3113847 http://zaguan.unizar.es/record/147040/files/texto_completo.jpg?subformat=icon icon Postprint oai:zaguan.unizar.es:147040 articulos driver 2026-02-17-20:46:28 ARTICLE