title: Influence of the N-N Coligand: C-C coupling instead of formation of imidazol-2-yl complexes at {Mo(η(3)-allyl)(CO)2} fragments. Theoretical and experimental studies.
abstract: New N-methylimidazole (N-MeIm) complexes of the {Mo(η(3)-allyl)(CO)2(N-N)} fragment have been prepared, in which the N,N-bidentate chelate ligand is a 2-pyridylimine. The addition of a strong base to the new compounds deprotonates the central CH group of the imidazole ligand and subsequently forms the C-C coupling product that results from the nucleophilic attack to the imine C atom. This reactivity contrasts with that previously found for the analogous 2,2'-bipyridine compounds [Mo(η(3)-allyl)(CO)2(bipy)(N-RIm)]OTf [N-RIm = N-MeIm, N-mesitylimidazole (N-MesIm, Mes= 2,4,6-trimethylphenyl); OTf = trifluoromethanesulfonate) which afforded imidazol-2-yl complexes upon deprotonation. Density Functional Theory (DFT) computations uncover that the reactivity of the imine C atom along with its ability to delocalize electron density are responsible for the new reactivity pattern found for the kind of molybdenum complexes reported herein.
authors.affiliation: Departamento de Química Inorgánica-ISQCH, Universidad de Zaragoza-CSIC , Pedro Cerbuna, 12, 50009 Zaragoza, Spain.
authors.forename: Andrea
authors.initials: A
authors.lastname: Cebollada
authors.forename: Maialen Espinal
authors.initials: ME
authors.lastname: Viguri
authors.forename: Julio
authors.initials: J
authors.lastname: Pérez
authors.forename: Jesús
authors.initials: J
authors.lastname: Díaz
authors.forename: Ramón
authors.initials: R
authors.lastname: López
authors.forename: Lucía
authors.initials: L
authors.lastname: Riera
mesh_terms: D007093:Imidazoles / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008968:Molecular Conformation; D008982:Molybdenum / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D011789:Quantum Theory
chemical_list: D007093:Imidazoles; D008024:Ligands; D009942:Organometallic Compounds; C029899:imidazole; D008982:Molybdenum