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.Reprinted (adapted) with permission from Inorganic Chemistry 39 (2000): 1301, doi:10.1021/ic990991l. Copyright 2000 American Chemical Society.</p
