Reactions of Titanium Imides and Hydrazides with Boranes

We report the first reactions of titanium imido, alkylidene hydrazido, and dimethylhydrazido compounds with the boranes H(2)BTex, 9-BBN, HBAr2F, and HBPin (Tex = tert-hexyl; Ar-F = C6F5). Reactions of Cp*TilMeC(NiPr)(2)}(NTol) withH(2)BTex, 9-BBN, or HBAr2F resulted in the hydride-bridged adducts Cp*Ti{MeC(N'Pr-2)(2)}{N(Tol)HBRR'} without B-H bondcleavage, Cp*Ti{MeC(NIPr)(2)}(NNCPh2) (4) reacted with HBAr2F via a sequence of steps involving adducts at the fi-and then a-nitrogen of the NNCPh2 ligand, before slow 1,2-addition of B-H across the N=CPh2 double bond of 4, forming Cp*Ti{MeC((NPr)-Pr-i)(2)}{NN(BAr2F)CHPh2} (17). The other boranes reacted immediately with 4 to form homologues of 17. These products are the first examples of borylhydrazido(2-) complexes. Reaction of cp*Ti{MeC(N'Pr-2)(2)}(NNMe2) (2) with HBAr2F gave the hydride-bridged adduct Cp*Ti{MeC((NPr2)-Pr-i)(2)}{N(NMe2)HBAr2F}, whereas with HBPin B-H bond cleavageoccurred to form the borylhydrazide(1-)-hydride Cp*Ti{MeC(NiPr)(2)}(H){N(BPin)NMe2}. Finally, reaction of 2 with 9-BBN clirner resulted in H-2 elimination and formation of Me2NBC8H14 and Cp*Ti{MeC(N'Pr)(2)}(NBC8H4), a rare example of a borylimido compound.