000078814 001__ 78814
000078814 005__ 20200811091507.0
000078814 0247_ $$2doi$$a10.1021/acs.inorgchem.8b00498
000078814 0248_ $$2sideral$$a106465
000078814 037__ $$aART-2018-106465
000078814 041__ $$aeng
000078814 100__ $$0(orcid)0000-0002-5465-4873$$aPuerta-Oteo, R.
000078814 245__ $$aZwitterionic Rhodium and Iridium Complexes Based on a Carboxylate Bridge-Functionalized Bis-N-heterocyclic Carbene Ligand: Synthesis, Structure, Dynamic Behavior, and Reactivity
000078814 260__ $$c2018
000078814 5060_ $$aAccess copy available to the general public$$fUnrestricted
000078814 5203_ $$aA series of water-soluble zwitterionic complexes featuring a carboxylate bridge-functionalized bis-N-heterocyclic carbene ligand of formula [Cp MIIICl{(MeIm)2CHCOO}] and [MI(diene){(MeIm)2CHCOO}] (Cp* = 1, 2, 3, 4, 5-pentamethylcyclopentadienyl; M = Rh, Ir; MeIm = 3-methylimidazol-2-yliden-1-yl; diene = 1, 5-cyclooctadiene (cod), norbornadiene (nbd)) were prepared from the salt [(MeImH)2CHCOO]Br and suitable metal precursor. The solid-state structure of both types of complexes shows a boat-shaped six-membered metallacycle derived of the ¿2C, C' coordination mode of the bis-NHC ligand. The uncoordinated carboxylate fragment is found at the bowsprit position in the Cp MIII complexes, whereas in the MI(diene) complexes it is at the flagpole position of the metallacycle. The complexes [RhI(diene){(MeIm)2CHCOO}] (diene = cod, nbd) exist as two conformational isomers in dichloromethane, bowsprit and flagpole, that interconvert through the boat-to-boat inversion of the metallacycle. An inversion barrier of ~17 kcal·mol-1 was determined by two-dimensional exchange spectroscopy NMR measurements for [RhI(cod){(MeIm)2CHCOO}]. Reaction of zwitterionic Cp MIII complexes with methyl triflate or tetrafluoroboric acid affords the cationic complexes [Cp MIIICl{(MeIm)2CHCOOMe}]+ or [Cp MIIICl{(MeIm)2CHCOOH}]+ (M = Rh, Ir) featuring carboxy and methoxycarbonyl functionalized methylene-bridged bis-NHC ligands, respectively. Similarly, complexes [MI(diene){(MeIm)2CHCOOMe}]+ (M = Rh, Ir) were prepared by alkylation of the corresponding zwitterionic MI(diene) complexes with methyl triflate. In contrast, reaction of [IrI(cod){(MeIm)2CHCOO}] with HBF4·Et2O (Et = ethyl), CH3OTf, CH3I, or I2 gives cationic iridium(III) octahedral complexes [IrIIIX(cod){(MeIm)2CHCOO}]+ (X = H, Me, or I) featuring a tripodal coordination mode of the carboxylate bridge-functionalized bis-NHC ligand. The switch from ¿2C, C' to ¿3C, C', O coordination of the bis-NHC ligand accompanying the oxidative addition prevents the coordination of the anions eventually formed in the process that remain as counterions.
000078814 536__ $$9info:eu-repo/grantAgreement/ES/DGA/E07$$9info:eu-repo/grantAgreement/ES/MINECO/BES-2011-045364$$9info:eu-repo/grantAgreement/ES/MINECO-FEDER/CTQ2016-75884-P
000078814 540__ $$9info:eu-repo/semantics/openAccess$$aAll rights reserved$$uhttp://www.europeana.eu/rights/rr-f/
000078814 590__ $$a4.85$$b2018
000078814 591__ $$aCHEMISTRY, INORGANIC & NUCLEAR$$b4 / 45 = 0.089$$c2018$$dQ1$$eT1
000078814 592__ $$a1.501$$b2018
000078814 593__ $$aChemistry (miscellaneous)$$c2018$$dQ1
000078814 593__ $$aPhysical and Theoretical Chemistry$$c2018$$dQ1
000078814 593__ $$aInorganic Chemistry$$c2018$$dQ1
000078814 655_4 $$ainfo:eu-repo/semantics/article$$vinfo:eu-repo/semantics/submittedVersion
000078814 700__ $$0(orcid)0000-0002-0545-9107$$aJiménez, M.V.$$uUniversidad de Zaragoza
000078814 700__ $$0(orcid)0000-0001-8054-2237$$aLahoz, F.J.$$uUniversidad de Zaragoza
000078814 700__ $$0(orcid)0000-0002-9633-3285$$aModrego, F.J.$$uUniversidad de Zaragoza
000078814 700__ $$0(orcid)0000-0002-1735-6439$$aPassarelli, V.
000078814 700__ $$0(orcid)0000-0002-3327-0918$$aPérez-Torrente, J.J.$$uUniversidad de Zaragoza
000078814 7102_ $$12010$$2760$$aUniversidad de Zaragoza$$bDpto. Química Inorgánica$$cÁrea Química Inorgánica
000078814 773__ $$g57, 9 (2018), 5526-5543$$pInorg. chem.$$tInorganic Chemistry$$x0020-1669
000078814 8564_ $$s1253860$$uhttps://zaguan.unizar.es/record/78814/files/texto_completo.pdf$$yPreprint
000078814 8564_ $$s127609$$uhttps://zaguan.unizar.es/record/78814/files/texto_completo.jpg?subformat=icon$$xicon$$yPreprint
000078814 909CO $$ooai:zaguan.unizar.es:78814$$particulos$$pdriver
000078814 951__ $$a2020-08-11-09:03:00
000078814 980__ $$aARTICLE