Abstract
We report the first reactions of titanium imido, alkylidene hydrazido, and dimethylhydrazido compounds with theboranes H 2 BTex, 9-BBN, HBAr F2 , and HBPin (Tex = tert-hexyl; Ar F = C 6 F 5 ). Reactions of Cp*Ti{MeC(N i Pr) 2 }(NTol) withH 2 BTex, 9-BBN, or HBAr F2 resulted in the hydride-bridged adducts Cp*Ti{MeC(N i Pr 2 ) 2 }{N(Tol)HBRR′} without B−H bondcleavage. Cp*Ti{MeC(N i Pr) 2 }(NNCPh 2 ) (4) reacted with HBAr F2 via a sequence of steps involving adducts at the β- and thenα-nitrogen of the NNCPh 2 ligand, before slow 1,2-addition of B−H across the NCPh 2 double bond of 4, formingCp*Ti{MeC(N i Pr) 2 }{NN(BAr F2 )CHPh 2 } (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 i Pr 2 ) 2 }(NNMe 2 ) (2) withHBAr F2 gave the hydride-bridged adduct Cp*Ti{MeC(N i Pr 2 ) 2 }{N(NMe 2 )HBAr F2 }, whereas with HBPin B−H bond cleavageoccurred to form the borylhydrazide(1-)-hydride Cp*Ti{MeC(N i Pr) 2 }(H){N(BPin)NMe 2 }. Finally, reaction of 2 with 9-BBNdimer resulted in H 2 elimination and formation of Me 2 NBC 8 H 14 and Cp*Ti{MeC(N i Pr) 2 }(NBC 8 H 14 ), a rare example of aborylimido compound.