title: Effect of the nature of the substituent in N-alkylimidazole ligands on the outcome of deprotonation: ring opening versus the formation of N-heterocyclic carbene complexes.
abstract: Complexes [Re(CO)(3)(N-RIm)(3)]OTf (N-RIm=N-alkylimidazole, OTf=trifluoromethanesulfonate; 1a-d) have been straightforwardly synthesised from [Re(OTf)(CO)(5)] and the appropriate N-alkylimidazole. The reaction of compounds 1a-d with the strong base KN(SiMe(3))(2) led to deprotonation of a central C-H group of an imidazole ligand, thus affording very highly reactive derivatives. The latter can evolve through two different pathways, depending on the nature of the substituents of the imidazole ligands. Compound 1a contains three N-MeIm ligands, and its product 2a features a C-bound imidazol-2-yl ligand. When 2a is treated with HOTf or MeOTf, rhenium N-heterocyclic carbenes (NHCs) 3a or 4a are afforded as a result of the protonation or methylation, respectively, of the non-coordinated N atom. The reaction of 2a with [AuCl(PPh(3))] led to the heterobimetallic compound 5, in which the N-heterocyclic ligand is once again N-bound to the Re atom and C-coordinated to the gold fragment. For compounds 1b-d, with at least one N-arylimidazole ligand, deprotonation led to an unprecedented reactivity pattern: the carbanion generated by the deprotonation of the C2-H group of an imidazole ligand attacks a central C-H group of a neighbouring N-RIm ligand, thus affording the product of C-C coupling and ring-opening of the imidazole moiety that has been attacked (2c, d). The new complexes featured an amido-type N atom that can be protonated or methylated, thus obtaining compounds 3c, d or 4c, d, respectively. The latter reaction forces a change in the disposition of the olefinic unit generated by the ring-opening of the N-RIm ligand from a cisoid to a transoid geometry. Theoretical calculations help to rationalise the experimental observation of ring-opening (when at least one of the substituents of the imidazole ligands is an aryl group) or tautomerisation of the N-heterocyclic ligand to afford the imidazol-2-yl product.
authors.affiliation: Departamento de Química Orgánica e Inorgánica-IUQOEM, Facultad de Química, Universidad de Oviedo-CSIC, 33006 Oviedo, Spain.
authors.forename: Miguel A
authors.initials: MA
authors.lastname: Huertos
authors.forename: Julio
authors.initials: J
authors.lastname: Pérez
authors.forename: Lucía
authors.initials: L
authors.lastname: Riera
authors.forename: Jesús
authors.initials: J
authors.lastname: Díaz
authors.forename: Ramón
authors.initials: R
authors.lastname: López
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007093:Imidazoles / Q000737:chemistry*; D008024:Ligands; D008697:Methane / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D012211:Rhenium / Q000737:chemistry*
chemical_list: D000475:Alkenes; D000588:Amines; D007093:Imidazoles; D008024:Ligands; D009942:Organometallic Compounds; C030011:carbene; D012211:Rhenium; D008697:Methane