ALKOXIDO, AMIDO, AND IMIDO DERIVATIVES OF TITANIUM(IV) TETRATOLYLPORPHYRIN

Treatment of (TTP)TiCl2 (1) [TTP = meso-5,10,15,20-tetra-p-tolylporphy rinato dianion] with excess NaOR (R = Ph, Me, t-Bu) affords the bis(al koxide) derivatives (TTP)Ti(OR)(2) [R = Ph (2), Me (3), t-Bu (4)] in m oderate yield. The corresponding amido derivative (TTP)Ti(NPh(2))(2) ( 5) is prepared in an analogous fashion employing LiNPh(2). The disubst ituted complexes 2, 3, and 5 react cleanly with (TTP)TiCl2 to afford t he ligand exchange products (TTP)Ti(OR)Cl [R = Ph (6), Me (7)] and (TT P)Ti(NPh(2))Cl (8), respectively. The monosubstituted complexes 6-8 ar e also obtained by treatment of 1 with 1 equiv of the appropriate NaOR or LiNPh(2) reagent. Treatment of 5 with excess phenol produces the b is(phenoxide) derivative 2 and 2 equiv of HNPh(2). The imido derivativ es (TTP)Ti = NR[R = t-Bu (9), Ph (10), C6H4-p-Me (11)] are prepared by the treatment of 1 with excess LiNHR. The t-Bu derivative (9) is also obtained by reaction of 1 with excess H2N-t-Bu at elevated temperatur es. The phenyl imido complex (10) may be produced by the reaction of 0 .5 equiv of PhN = NPh with (TTP)Ti(eta(2)-EtC = CEt) in refluxing tolu ene. Finally, (TTP)Ti = NTMS (12) is obtained by oxidation of (TTP)Ti( eta(2)-EtC = CEt) with N(3)TMS.