Deprotonation Reactions of Zirconium and Hafnium Amide Complexes H₂N−M[N(SiMe₃)₂]₃ and Subsequent Silyl Migration from Amide −N(SiMe₃)₂ to Imide NH Ligands

Ammonolysis of previously reported Cl−M[N(SiMe3)2]3 (M = Zr, 1a; Hf, 1b) leads to the formation of peramides H2N−M[N(SiMe3)2]3 (M = Zr, 2a; Hf, 2b) which upon deprotonation by LiN(SiMe3)2 or Li(THF)3SiPh2But yields imides Li+(THF)n{HN-−M[N(SiMe3)2]3} (M = Zr, 3a; Hf, 3b). One −SiMe3 group in 3a−b undergoes silyl migration from a −N(SiMe3)2 ligand to the imide NH ligand to give Li+(THF)2{Me3SiN-−M[NH(SiMe3)][N(SiMe3)2]2} (M = Zr, 4a; Hf, 4b) containing an imide N(SiMe3) ligand. The kinetics of the 3a → 4a conversion was investigated between 290 and 315 K and was first-order with respect to 3a. The activation parameters for this silyl migration are ΔH‡ = 13.3(1.3) kcal/mol and ΔS‡ = −34(3) eu in solutions of 3a (in toluene-d8 with 1.07 M THF) prepared in situ. THF in the mixed solvent promoted the 3a → 4a reaction. The effect of THF on the rate constants of the conversion has been studied, and the kinetics of the reaction was 3.4(0.6)th order with respect to THF. Crystal and molecular structures of H2N−Zr[N(SiMe3)2]3 (2a) and 4a−b have been determined.