Jl. Thorman et Lk. Woo, Synthesis and reactivity of hydrazido(2-) and imido derivatives of titanium(IV) tetratolylporphyrin, INORG CHEM, 39(6), 2000, pp. 1301-1304
Titanium porphyrin hydrazido complexes (TTP)Ti=NNR2 (TTP = meso-tetra-p-tol
ylporphyrinato dianion; R = Me (1), Ph (2)) were synthesized by treatment o
f (TTP)TiCl2 with 1,1-disubstituted hydrazines H2NNR2 (R Me, Ph) in the pre
sence of piperidine. The nucleophilic character of the hydrazido moiety was
demonstrated in the reactions of complexes 1 and 2 with p-chlorobenzaldehy
de, which yielded the titanium oxo complex (TTP)Ti=O and the respective hyd
razones. Protonation of complexes 1 and 2 with phenol or water produced the
1,1-disubstituted hydrazine along with (TTP)Ti(OPh)(2) or (TTP)Ti=O, respe
ctively. Similar reactivity of p-chlorobenzaldehyde and phenol with (TTP)Ti
=(NPr)-Pr-i, 3, was observed. The reaction of complex 3 with nitrosobenzene
cleanly formed the azo compound (PrN)-Pr-i=NPh and the terminal oxo produc
t (TTP)Ti=O.