000165848 001__ 165848
000165848 005__ 20260119151008.0
000165848 0247_ $$2doi$$a10.1021/acs.organomet.1c00453
000165848 0248_ $$2sideral$$a127203
000165848 037__ $$aART-2021-127203
000165848 041__ $$aeng
000165848 100__ $$0(orcid)0000-0003-2249-6054$$aHermosilla P.$$uUniversidad de Zaragoza
000165848 245__ $$aRh Complexes with Pincer Carbene CNC Lutidine-Based Ligands: Reactivity Studies toward H2 Addition
000165848 260__ $$c2021
000165848 5060_ $$aAccess copy available to the general public$$fUnrestricted
000165848 5203_ $$aLutidine-based NHCs pincer precursors CNCMe and CNCMes were combined with [Rh(acac)(nbd)] (acac = acetylacetonate; nbd = 2, 5-norbornadiene) in the presence of Cs2CO3 to yield complexes [(CNC)MeRh(nbd)]PF6 (3) and [(CNC)MesRh(NCMe)]PF6 (4), respectively. While in 3, the nbd diolefin remains coordinated, in 4, the voluminous mesityl ligands induce nbd decoordination, so acetonitrile stabilizes Rh(I) adduct 4, which in turn undergoes substitution reactions with a number of neutral ligands to produce cationic complexes [(CNC)MesRh(L)]PF6 (L = CO (5), PMe2Ph (6), PEt3 (7), C2H4 (8)). These complexes have been studied through VT NMR measurements and the molecular structures by X-ray crystallography in the case of adducts 4-7. Deprotonation reactions on cationic complexes 3-6 with hard bases yielded the corresponding neutral complexes [(CNC)*MeRh(nbd)] (9) and mesityl derivatives [(CNC)*MesRh(L)] (L = NCCH3 (10), CO (11), PMe2Ph (12)), all of which are dearomatized complexes due to the deprotonation of one of the methylene arms, a situation confirmed by the X-ray molecular structure of carbonyl adduct 5. We studied the reactivity toward dihydrogen with neutral adducts 11 and 12. The electron rich phosphane 12 adds H2 through oxidative addition, affording the bis(hydrido) Rh(III) complex [(CNC)*MesRh(PMe2Ph)H2] (14). However, the carbonyl adduct 11 reacts with H2 in a different way, so that the central pyridinic ring becomes hydrogenated, breaking the aromaticity and leading to complex [(CNC-H2)*MesRh(CO)] (13), isolated as a mixture of two isomers. DFT studies were carried out in order to establish the mechanisms followed on these hydrogenations, finding that, while the phosphane adduct reacts following an oxidative addition mechanism, the carbonyl complex follows a more complex base-induced profile due to the instability of hydride carbonyl species. © 2021 American Chemical Society.
000165848 536__ $$9info:eu-repo/grantAgreement/ES/DGA-FSE/E42-20R$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/PGC2018-099383-B-I00
000165848 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000165848 590__ $$a3.837$$b2021
000165848 591__ $$aCHEMISTRY, ORGANIC$$b15 / 56 = 0.268$$c2021$$dQ2$$eT1
000165848 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b12 / 46 = 0.261$$c2021$$dQ2$$eT1
000165848 592__ $$a0.994$$b2021
000165848 593__ $$aOrganic Chemistry$$c2021$$dQ1
000165848 593__ $$aInorganic Chemistry$$c2021$$dQ1
000165848 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/acceptedVersion
000165848 700__ $$0(orcid)0000-0002-7063-1292$$aGarcía-Orduña P.
000165848 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz F.J.
000165848 700__ $$0(orcid)0000-0001-5823-7965$$aPolo V.$$uUniversidad de Zaragoza
000165848 700__ $$0(orcid)0000-0003-1707-3022$$aCasado M.A.$$uUniversidad de Zaragoza
000165848 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000165848 7102_ $$12012$$2755$$aUniversidad de Zaragoza$$bDpto. Química Física$$cÁrea Química Física
000165848 773__ $$g40, 22 (2021), 3720-3732$$pOrganometallics$$tOrganometallics$$x0276-7333
000165848 8564_ $$s888503$$uhttps://zaguan.unizar.es/record/165848/files/texto_completo.pdf$$yPostprint
000165848 8564_ $$s3033000$$uhttps://zaguan.unizar.es/record/165848/files/texto_completo.jpg?subformat=icon$$xicon$$yPostprint
000165848 909CO $$ooai:zaguan.unizar.es:165848$$particulos$$pdriver
000165848 951__ $$a2026-01-19-15:09:29
000165848 980__ $$aARTICLE