000150373 001__ 150373
000150373 005__ 20250203171510.0
000150373 0247_ $$2doi$$a10.1021/acs.inorgchem.2c00617
000150373 0248_ $$2sideral$$a129199
000150373 037__ $$aART-2022-129199
000150373 041__ $$aeng
000150373 100__ $$0(orcid)0000-0003-2249-6054$$aHermosilla, P.$$uUniversidad de Zaragoza
000150373 245__ $$aNucleophilic Reactivity at a=CH Arm of a Lutidine-Based CNC/Rh System: Unusual Alkyne and CO2Activation; 35476902
000150373 260__ $$c2022
000150373 5060_ $$aAccess copy available to the general public$$fUnrestricted
000150373 5203_ $$aReaction of an amido pincer complex (CNC)*Rh(CO)] (1) (CNC* is the deprotonated form of CNC) with carbon dioxide gave a neutral complex (CNC-CO2)Mes*Rh(CO)] (2), which is the result of a C-C bond-forming reaction between the deprotonated arm of the CNC* ligand and CO2. The molecular structure of 2 showed a zwitterionic complex, where the CO2 moiety is covalently connected to the former =CH arm of the CNC* pincer ligand. The unusual structure of 1 allowed us to explore the reactivity of the CO2 moiety with selected primary amines RNH2 (benzylamine and ammonia), which afforded cationic complexes (CNC)MesRh(CO)]HRNC(O)O] (R = Bz (3), H (4)). Compounds 3 and 4 are the result of a C-N coupling between the incoming amine and the CO2 fragment covalently connected to the pincer ligand in 2, a process that involves protonation of the "CH-CO2"fragment in 2 from the respective amines. Once revealed the nucleophilic character of the =CH fragment in 1, we explored its reactivity with alkynes, a study that enlightened a novel reactivity trend in alkyne activation. Reaction of 1 with terminal alkynes RCCH (R = Ph, 2-py, 4-C6H4-CF3) yielded neutral complexes (CNC-CH=CHR)Mes*Rh(CO)] (R = Ph (5), 2-py (6), 4-C6H4-CF3 (7)) in good yields. Deuterium labeling experiments with PhCCD confirmed that complex 5 is the product of a formal insertion of the alkyne into the C(sp2)-H bond of the deprotonated arm in 1. This structural proposal was further confirmed by the X-ray molecular structure of phenyl complex 5, which showed the alkyne covalently linked to the pincer ligand. Besides, this novel transformation was analyzed by DFT methods and showed a metal-ligand cooperative mechanism, based on the initial electrophilic attack of the alkyne to the =CH arm of the CNCMes* ligand (making a new C-C bond) followed by the action of a protic base (HN(SiMe3)2), which is able to perform a proton rearrangement that leads to the final product 5. © 2022 American Chemical Society.
000150373 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00
000150373 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000150373 590__ $$a4.6$$b2022
000150373 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b5 / 42 = 0.119$$c2022$$dQ1$$eT1
000150373 592__ $$a0.997$$b2022
000150373 593__ $$aChemistry (miscellaneous)$$c2022$$dQ1
000150373 593__ $$aPhysical and Theoretical Chemistry$$c2022$$dQ1
000150373 593__ $$aInorganic Chemistry$$c2022$$dQ1
000150373 594__ $$a8.0$$b2022
000150373 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000150373 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña, P.
000150373 700__ $$0(orcid)0000-0002-8220-6031$$aSanz Miguel, P. J.$$uUniversidad de Zaragoza
000150373 700__ $$0(orcid)0000-0001-5823-7965$$aPolo, V.$$uUniversidad de Zaragoza
000150373 700__ $$0(orcid)0000-0003-1707-3022$$aCasado, M. A.$$uUniversidad de Zaragoza
000150373 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000150373 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000150373 773__ $$g66, 18 (2022), 7120–7129$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000150373 8564_ $$s856204$$uhttps://zaguan.unizar.es/record/150373/files/texto_completo.pdf$$yPostprint
000150373 8564_ $$s1732405$$uhttps://zaguan.unizar.es/record/150373/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000150373 909CO $$ooai:zaguan.unizar.es:150373$$particulos$$pdriver
000150373 951__ $$a2025-02-03-14:49:50
000150373 980__ $$aARTICLE