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Título: | Zwitterionic rhodium and iridium complexes based on a carboxylate bridge-functionalized bis-N-heterocyclic carbene ligand: Synthesis, structure, dynamic behavior, and reactivity |
Autor: | Puerta-Oteo, Raquel CSIC; Jiménez, M. Victoria CSIC ORCID ; Lahoz, Fernando J. CSIC ORCID; Modrego, Francisco J. CSIC ORCID; Passarelli, Vincenzo CSIC ORCID; Pérez-Torrente, Jesús J. CSIC ORCID | Fecha de publicación: | 2018 | Editor: | American Chemical Society | Citación: | Inorganic Chemistry 57(9): 5526-5543 (2018) | Resumen: | 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. | Versión del editor: | https://doi.org/10.1021/acs.inorgchem.8b00498 | URI: | http://hdl.handle.net/10261/177148 | DOI: | 10.1021/acs.inorgchem.8b00498 | Identificadores: | doi: 10.1021/acs.inorgchem.8b00498 e-issn: 1520-510X issn: 0020-1669 |
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