Journal or Book Title
Titanium porphyrin hydrazido complexes (TTP)TiNNR2 (TTP = meso-tetra-p-tolylporphyrinato dianion; R = Me (1), Ph (2)) were synthesized by treatment of (TTP)TiCl2with 1,1-disubstituted hydrazines H2NNR2 (R = Me, Ph) in the presence of piperidine. The nucleophilic character of the hydrazido moiety was demonstrated in the reactions of complexes 1 and 2 with p-chlorobenzaldehyde, which yielded the titanium oxo complex (TTP)TiO and the respective hydrazones. Protonation of complexes 1 and 2 with phenol or water produced the 1,1-disubstituted hydrazine along with (TTP)Ti(OPh)2 or (TTP)TiO, respectively. Similar reactivity of p-chlorobenzaldehyde and phenol with (TTP)TiNiPr, 3, was observed. The reaction of complex 3 with nitrosobenzene cleanly formed the azo compound iPrNNPh and the terminal oxo product (TTP)TiO.
American Chemical Society
Thorman, Joseph Lyndon and Woo, L. Keith, "Synthesis and Reactivity of Hydrazido(2-) and Imido Derivatives of Titanium(IV) Tetratolylporphyrin" (2000). Chemistry Publications. 762.