New Titanium Borylimido Compounds: Synthesis, Structure, and Bonding

We report a combined experimental and computational study of the synthesis and electronic structure of titanium borylimido compounds. Three new synthetic routes to this hitherto almost unknown class of Group 4 imide are presented. The double-deprotonation reaction of the borylamine H₂NB(NAr'CH)₂ (Ar' = 2,6-C₆H₃ⁱPr₂) with Ti(NMe₂)₂Cl₂ gave Ti{NB(NAr'CH)₂}Cl₂(NHMe₂)₂, which was easily converted to Ti{NB(NAr'CH)₂}Cl₂(py)₃. This compound is an entry point to other borylimides, for example, reacting with Li₂N₂^pyrN^Me to form Ti(N₂^pyrN^Me){NB(NAr'CH)₂}(py)₂ and with 2 equiv of NaCp to give Cp₂Ti{NB(NAr'CH)₂}(py) (23). Borylamine-tert-butylimide exchange between H₂NB(NAr'CH)₂ and Cp*Ti(N^tBu)Cl(py) under forcing conditions afforded Cp*Ti{NB(NAr'CH)₂}Cl(py), which could be further substituted with guanidinate or pyrrolide-amine ligands to give Cp*Ti(hpp){NB(NAr'CH)₂} (16) and Cp*Ti(N^pyrN^Me){NB(NAr'CH)₂} (17). The Ti-N_im distances in compounds with the NB(NAr'CH)₂ ligand were comparable to those of the corresponding arylimides. Dialkyl- or diaryl-substituted borylamines do not undergo the analogous double-deprotonation or imide-amine exchange reactions. Reaction of (Cp″₂Ti)₂(μ₂:η¹,η¹-N₂) with N₃BMes₂ gave the base-free, diarylborylimide Cp″₂Ti(NBMes₂) (26) by an oxidative route; this compound has a relatively long Ti-N_im bond and large Cp″-Ti-Cp″ angle. Reaction of 16 with H₂N^tBu formed equilibrium mixtures with H₂NB(NAr'CH)₂ and Cp*Ti(hpp)(N^tBu) (Δ_rG = -1.0 kcal mol^-1). In contrast, the dialkylborylimide Cp*Ti{MeC(NⁱPr)₂}(NBC₈H₁₄) (2) reacted quantitatively with H₂N^tBu to give the corresponding tert-butylimide and borylamine. The electronic structures and imide-amine exchange reactions of half-sandwich and sandwich titanium borylimides have been evaluated using density functional theory (DFT), supported by quantum theory of atoms in molecules (QTAIM) and natural bond orbital (NBO) analysis, and placed more generally in context with the well-established alkyl- and arylimides and hydrazides. The calculations find that Ti-N_im bonds for borylimides are stronger and more covalent than in their organoimido or hydrazido analogues, and are strongest for alkyl- and arylborylimides. Borylamine-tert-butylimide exchange reactions fail for H₂NBR₂ (R = hydrocarbyl) but not for H₂NB(NAr'CH)₂ because the increased strength of the new Ti-N_im bond for the former is outweighed by the increased net H-N bond strengths in the borylamine. Variation of the Ti-N_im bond length over short distances is dominated by π-interactions with any appropriate orbital on the N_im atom organic substituent. However, over the full range of imides and hydrazides studied, overall bond energies do not correlate with bond length but with the Ti-N_im σ-bond character and the orthogonal π-interaction.