Synthesis and reactivity of hydrazido(2-) and imido derivatives of titanium(IV) tetratolylporphyrin

Citation
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
Citations number
31
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
INORGANIC CHEMISTRY
ISSN journal
00201669 → ACNP
Volume
39
Issue
6
Year of publication
2000
Pages
1301 - 1304
Database
ISI
SICI code
0020-1669(20000320)39:6<1301:SAROHA>2.0.ZU;2-R
Abstract
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.