3 years ago

Reactions of Titanium Imides and Hydrazides with Boranes

Reactions of Titanium Imides and Hydrazides with Boranes
Simona Mellino, Philip Mountford, Eric Clot, Laura C. Stevenson
We report the first reactions of titanium imido, alkylidene hydrazido, and dimethylhydrazido compounds with the boranes H2BTex, 9-BBN, HBArF2, and HBPin (Tex = tert-hexyl; ArF = C6F5). Reactions of Cp*Ti{MeC(NiPr)2}(NTol) with H2BTex, 9-BBN, or HBArF2 resulted in the hydride-bridged adducts Cp*Ti{MeC(NiPr2)2}{N(Tol)HBRR′} without B–H bond cleavage. Cp*Ti{MeC(NiPr)2}(NNCPh2) (4) reacted with HBArF2 via a sequence of steps involving adducts at the β- and then α-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(NiPr)2}{NN(BArF2)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(NiPr2)2}(NNMe2) (2) with HBArF2 gave the hydride-bridged adduct Cp*Ti{MeC(NiPr2)2}{N(NMe2)HBArF2}, whereas with HBPin B–H bond cleavage occurred to form the borylhydrazide(1-)-hydride Cp*Ti{MeC(NiPr)2}(H){N(BPin)NMe2}. Finally, reaction of 2 with 9-BBN dimer resulted in H2 elimination and formation of Me2NBC8H14 and Cp*Ti{MeC(NiPr)2}(NBC8H14), a rare example of a borylimido compound.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00477

DOI: 10.1021/acs.organomet.7b00477

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