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 HNB(NAr'CH) (Ar' = 2,6-CHPr) with Ti(NMe)Cl gave Ti{NB(NAr'CH)}Cl(NHMe), which was easily converted to Ti{NB(NAr'CH)}Cl(py).

New Scandium Borylimido Chemistry: Synthesis, Bonding, and Reactivity.

We report a combined synthetic, mechanistic, and theoretical study of the first borylimido complex of a rare earth metal, (NacNac)Sc{NB(NAr'CH)} (25, Ar' = 2,6-CHPr, NacNac = Ar'NC(Me)CHC(Me)NCHCHNMe). Thermolysis of the methyl-borylamide (NacNac)Sc(Me){NHB(NAr'CH)} (18) generated transient imide 25 via rate-determining, first-order methane elimination (KIE ≈ 8.7).