000147040 001__ 147040
000147040 005__ 20241205091043.0
000147040 0247_ $$2doi$$a10.1021/acs.organomet.4c00409
000147040 0248_ $$2sideral$$a140734
000147040 037__ $$aART-2024-140734
000147040 041__ $$aeng
000147040 100__ $$aEspañol-Sánchez, Belinda
000147040 245__ $$aTuning the pyridone scaffold within a Rhodium-NHC platform for gem-specific alkyne dimerization via a ligand-assisted proton shuttle mechanism
000147040 260__ $$c2024
000147040 5060_ $$aAccess copy available to the general public$$fUnrestricted
000147040 5203_ $$aA 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.
000147040 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E42-23R$$9info:eu-repo/grantAgreement/ES/MECD/FPU17-05417$$9info:eu-repo/grantAgreement/ES/MICINN/PID2019-103965GB-I00/AEI/10.13039/501100011033$$9info:eu-repo/grantAgreement/ES/MICINN/PID2022-137208NB-I00
000147040 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc-nd$$uhttp://creativecommons.org/licenses/by-nc-nd/3.0/es/
000147040 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000147040 700__ $$0(orcid)0000-0002-2043-4864$$aGaliana-Cameo, María$$uUniversidad de Zaragoza
000147040 700__ $$0(orcid)0000-0001-9352-6922$$aUrriolabeitia, Asier$$uUniversidad de Zaragoza
000147040 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, Victor$$uUniversidad de Zaragoza
000147040 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, Vincenzo
000147040 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, Jesús J.$$uUniversidad de Zaragoza
000147040 700__ $$0(orcid)0000-0003-4460-8678$$aCastarlenas, Ricardo
000147040 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000147040 7102_ $$12013$$2765$$aUniversidad de Zaragoza$$bDpto. Química Orgánica$$cÁrea Química Orgánica
000147040 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000147040 773__ $$g43, 22 (2024), 2951-2962$$pOrganometallics$$tOrganometallics$$x0276-7333
000147040 8564_ $$s1442269$$uhttps://zaguan.unizar.es/record/147040/files/texto_completo.pdf$$yPostprint
000147040 8564_ $$s3113847$$uhttps://zaguan.unizar.es/record/147040/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000147040 909CO $$ooai:zaguan.unizar.es:147040$$particulos$$pdriver
000147040 951__ $$a2024-12-05-08:47:06
000147040 980__ $$aARTICLE