000124379 001__ 124379 000124379 005__ 20250210083428.0 000124379 0247_ $$2doi$$a10.1039/d2ra06982b 000124379 0248_ $$2sideral$$a132734 000124379 037__ $$aART-2022-132734 000124379 041__ $$aeng 000124379 100__ $$aTejero, Alvaro G.$$uUniversidad de Zaragoza 000124379 245__ $$aSynthesis of chiral-at-metal rhodium complexes from achiral tripodal tetradentate ligands: resolution and application to enantioselective Diels–Alder and 1,3-dipolar cycloadditions 000124379 260__ $$c2022 000124379 5060_ $$aAccess copy available to the general public$$fUnrestricted 000124379 5203_ $$aAn improved synthesis of the racemic rhodium compound [RhCl2(κ4C,N,N′,P-L1)] (1) containing an achiral tripodal tetradentate ligand is reported. Their derived solvate complexes [Rh(κ4C,N,N′,P-L1)(Solv)2][SbF6]2 (Solv = NCMe, 2; H2O, 3) are resolved into their two enantiomers. Complexes 2 and 3 catalyze the Diels–Alder (DA) reaction between methacrolein and cyclopentadiene and the 1,3-dipolar cycloaddition reaction between methacrolein and the nitrone N-benzylidenphenylamine-N-oxide. When enantiopure (ARh,RN)-2 was employed as the catalyst, enantiomeric ratios >99/1, in the R at C2 adduct, and up to 94/6, in the 3,5-endo isomer, were achieved in the DA reaction and in the 1,3-dipolar cycloaddition reaction, respectively. A plausible catalytic cycle that accounts for the origin of the observed enantioselectivity is proposed. 000124379 536__ $$9info:eu-repo/grantAgreement/ES/MICINN/CTQ2018-095561-BI00$$9info:eu-repo/grantAgreement/ES/MCIU-AEI-FEDER/PID2021-122406NB-I00$$9info:eu-repo/grantAgreement/ES/DGA/E05-20R 000124379 540__ $$9info:eu-repo/semantics/openAccess$$aby-nc$$uhttp://creativecommons.org/licenses/by-nc/3.0/es/ 000124379 590__ $$a3.9$$b2022 000124379 592__ $$a0.678$$b2022 000124379 591__ $$aCHEMISTRY, MULTIDISCIPLINARY$$b74 / 178 = 0.416$$c2022$$dQ2$$eT2 000124379 593__ $$aChemistry (miscellaneous)$$c2022$$dQ2 000124379 593__ $$aChemical Engineering (miscellaneous)$$c2022$$dQ2 000124379 594__ $$a6.8$$b2022 000124379 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/publishedVersion 000124379 700__ $$aCarmona, María 000124379 700__ $$0(orcid)0000-0002-8845-0174$$aRodríguez, Ricardo 000124379 700__ $$0(orcid)0000-0002-6160-3046$$aViguri, Fernando$$uUniversidad de Zaragoza 000124379 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, Fernando J. 000124379 700__ $$aGarcía-Orduña, Pilar 000124379 700__ $$0(orcid)0000-0003-4196-5856$$aCarmona, Daniel 000124379 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica 000124379 773__ $$g12, 53 (2022), 34704-34714$$pRSC ADVANCES$$tRSC Advances$$x2046-2069 000124379 8564_ $$s1222651$$uhttps://zaguan.unizar.es/record/124379/files/texto_completo.pdf$$yVersión publicada 000124379 8564_ $$s2909885$$uhttps://zaguan.unizar.es/record/124379/files/texto_completo.jpg?subformat=icon$$xicon$$yVersión publicada 000124379 909CO $$ooai:zaguan.unizar.es:124379$$particulos$$pdriver 000124379 951__ $$a2025-02-10-08:31:19 000124379 980__ $$aARTICLE