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 fac → mer rearrangement of the tridentate ligand. Two routes have
been explored for the overall migratory insertion process, depending
on the order of the fac → mer and insertion steps. Calculations show that the dissociative (first fac → mer rearrangement, then migratory
insertion) and the associative (first migratory insertion, then fac → mer 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 fac → mer interconversion.