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Rearrangement of Tridentate [OSO]-Type Ligands and Migratory Insertion Reaction Mechanisms in Cyclopentadienyl Tantalum Complexes

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journal contribution
posted on 22.10.2012, 00:00 by Jacob Fernández-Gallardo, Luca Bellarosa, Gregori Ujaque, Agustí Lledós, María José Ruiz, Rosa Fandos, Antonio Otero
The mechanism of the isocyanide migratory insertion into the metal–carbon bond of monocylopentadienyltantalum dimethyl derivatives with [OSO]2– tridentate phenolate ligands has been investigated with DFT calculations. The presence of both a cyclopentadienyl and a tridentate ligand complicates a usually simple reaction, the migratory insertion reaction being coupled with a facmer rearrangement of the tridentate ligand. Two routes have been explored for the overall migratory insertion process, depending on the order of the facmer and insertion steps. Calculations show that the dissociative (first facmer rearrangement, then migratory insertion) and the associative (first migratory insertion, then facmer rearrangement) pathways are in principle competitive. However, electronic effects of the phenyl substituents can favor one of the pathways. The study also points out the influence of the donor atom, due to the inversion at the donor atom required in order to achieve the facmer interconversion.