Lithium-Alkyl, -Aryl, and -Amido Ligand-Exchange Dynamics of Dianionic Zirconium(IV) Complexes with Chelating Amidophenolate Ligands

The synthesis, characterization, and solution behavior of a series of six-coordinate zirconium(IV) dianions [ZrX2(ap)2]2-
(ap = 2,4-di-tert-butyl-6-(tert-butylamido)phenolate; X = Ph, 3a; X = p-tolyl, 3b; X = Me, 4; X = NMe2, 5) are
described. Complexes 3−5 were prepared by treating the neutral zirconium complex Zr(ap)2(THF)2 (1) with 2 equiv
of LiX or by the direct reaction of apLi2 and LiX with ZrCl4. The complexes were isolated as lithium-etherate salts,
and they were characterized by NMR spectroscopy and single-crystal X-ray diffraction. In non-coordinating solvents
such as benzene-d6, complexes 3−5 are robust in solution, but in coordinating solvents such as THF-d8, dissociation
of LiX was observed. The rate of LiX loss was evaluated by exchange reactions; the reaction rate constants span
nine orders of magnitude at 298 K, with the slowest reaction being the dissociation of PhLi from 3a (τ1/2 = 4 h)
and the fastest reaction being the dissociation of LiNMe2 from 5 (τ1/2 = 53 μs). In the case of LiNMe2 dissociation
from 5, activation parameters suggest that the rate-determining step is purely dissociative; however, for diphenyl
and dimethyl complexes 3a and 4, respectively, activation parameters suggest a solvent-assisted rate-determining
step.