Alkoxido, Amido, and Imido Derivatives of Titanium(IV) TetratolylporphyrinInorganic Chemistry
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AbstractTreatment of (TTP)TiCl2 (1) [TTP = meso-5,10,15,20-tetra-p-tolylporphyrinato dianion] with excess NaOR (R = Ph, Me, t-Bu) affords the bis(alkoxide) derivatives (TTP)Ti(OR)2 [R = Ph (2), Me (3), t-Bu (4)] in moderate yield. The corresponding amido derivative (TTP)Ti(NPh2)2(5) is prepared in an analogous fashion employing LiNPh2. The disubstituted complexes 2, 3, and 5 react cleanly with (TTP)TiCl2 to afford the ligand exchange products (TTP)Ti(OR)Cl [R = Ph (6), Me (7)] and (TTP)Ti(NPh2)Cl (8), respectively. The monosubstituted complexes 6−8are also obtained by treatment of 1 with 1 equiv of the appropriate NaOR or LiNPh2 reagent. Treatment of 5 with excess phenol produces the bis(phenoxide) derivative 2 and 2 equiv of HNPh2. The imido derivatives (TTP)TiNR [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 temperatures. The phenyl imido complex (10) may be produced by the reaction of 0.5 equiv of PhNNPh with (TTP)Ti(η2-EtC⋮CEt) in refluxing toluene. Finally, (TTP)TiNTMS (12) is obtained by oxidation of (TTP)Ti(η2-EtC⋮CEt) with N3TMS.
Copyright OwnerAmerican Chemical Society
Citation InformationSteven D. Gray, Joseph Lyndon Thorman, Lisa Mary Berreau and L. Keith Woo. "Alkoxido, Amido, and Imido Derivatives of Titanium(IV) Tetratolylporphyrin" Inorganic Chemistry Vol. 36 Iss. 3 (1997) p. 278 - 283
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