title: Synthesis and reactivity of hydrazido(2-) and imido derivatives of titanium(IV) tetratolylporphyrin.
abstract: Titanium porphyrin hydrazido complexes (TTP)Ti = NNR2 (TTP = meso-tetra-p-tolylporphyrinato dianion; R = Me (1), Ph (2)) were synthesized by treatment of (TTP)TiCl2 with 1,1-disubstituted hydrazines H2NNR2 (R = Me, Ph) in the presence of piperdine. 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)-Ti = O 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)Ti = O, respectively. Similar reactivity of p-chlorobenzaldehyde and phenol with (TTP)Ti = NiPr, 3, was observed. The reaction of complex 3 with nitrosobenzene cleanly formed the azo compound iPrN = NPh and the terminal oxo product (TTP)Ti = O.
authors.affiliation: Department of Chemistry, Iowa State University, Ames, Iowa 50011-3111, USA.
authors.forename: J L
authors.initials: JL
authors.lastname: Thorman
authors.forename: L K
authors.initials: LK
authors.lastname: Woo