Zwitterionic rhodium and iridium complexes based on a carboxylate bridge-functionalized bis-N-heterocyclic carbene ligand: Synthesis, structure, dynamic behavior, and reactivity
| Autor: | M. Victoria Jiménez, Jesús J. Pérez-Torrente, Vincenzo Passarelli, Fernando J. Lahoz, Raquel Puerta-Oteo, F. Javier Modrego |
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| Přispěvatelé: | Ministerio de Economía y Competitividad (España), European Commission, Diputación General de Aragón |
| Rok vydání: | 2018 |
| Předmět: |
Diene
010405 organic chemistry Ligand Norbornadiene Metallacycle 010402 general chemistry 01 natural sciences Medicinal chemistry 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound chemistry Reactivity (chemistry) Carboxylate Physical and Theoretical Chemistry Conformational isomerism Carbene |
| Zdroj: | Digital.CSIC. Repositorio Institucional del CSIC instname |
| Popis: | A series of water-soluble zwitterionic complexes featuring a carboxylate bridge-functionalized bis-N-heterocyclic carbene ligand of formula [Cp MCl{(MeIm)CHCOO}] and [M(diene){(MeIm)CHCOO}] (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)CHCOO]Br and suitable metal precursor. The solid-state structure of both types of complexes shows a boat-shaped six-membered metallacycle derived of the κC,C′ coordination mode of the bis-NHC ligand. The uncoordinated carboxylate fragment is found at the bowsprit position in the Cp M complexes, whereas in the M(diene) complexes it is at the flagpole position of the metallacycle. The complexes [Rh(diene){(MeIm)CHCOO}] (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 was determined by two-dimensional exchange spectroscopy NMR measurements for [Rh(cod){(MeIm)CHCOO}]. Reaction of zwitterionic Cp M complexes with methyl triflate or tetrafluoroboric acid affords the cationic complexes [Cp MCl{(MeIm)CHCOOMe}] or [Cp MCl{(MeIm)CHCOOH}] (M = Rh, Ir) featuring carboxy and methoxycarbonyl functionalized methylene-bridged bis-NHC ligands, respectively. Similarly, complexes [M(diene){(MeIm)CHCOOMe}] (M = Rh, Ir) were prepared by alkylation of the corresponding zwitterionic M(diene) complexes with methyl triflate. In contrast, reaction of [Ir(cod){(MeIm)CHCOO}] with HBF·EtO (Et = ethyl), CHOTf, CHI, or I gives cationic iridium(III) octahedral complexes [IrX(cod){(MeIm)CHCOO}] (X = H, Me, or I) featuring a tripodal coordination mode of the carboxylate bridge-functionalized bis-NHC ligand. The switch from κC,C′ to κC,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. Financial support from the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) under the Project CTQ2016-75884-P and the Diputación General de Aragón (DGA/FSE-E07) is gratefully acknowledged. R.P.-O. also thanks MINECO for a predoctoral fellowship (BES-2011-045364). |
| Databáze: | OpenAIRE |
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