Synthesis of unsymmetrically substituted antimony(V) tetraphenylporphyrins

Article abstract of DOI:10.1246/bcsj.72.459

The following nine unsymmetrically axially substituted antimony(V) tetraphenylporphyrins with an antimony-carbon bond or an antimony-fluorine bond were synthesized: [(TPP)Sb(Me)(OEt)]⁺ClO₄^- (1-ClO₄), [(TPP)Sb(Me)(OC₆H₄CH₃-p)]⁺ClO₄^- (2-ClO₄), [(TPP)Sb(Me)(SC₆H₄CH₃- p)]⁺ClO₄^- (3-ClO₄), [(TPP)Sb(Me)(NHC₆H₄CH₃-p)]⁺ClO₄^- (4-ClO₄), [(TPP)Sb(Me)(NHCH₂C₆H₅)]⁺ClO₄^- (5-ClO₄), [(TPP)Sb(Me)(OC(=O)C₆H₄Cl- m)]⁺PF₆^- (6-PF₆), [(TPP)Sb(Me)(Et)]⁺PF₆^- (7-PF₆), [(TPP)Sb(Me)(CH₂CHMe₂)]⁺PF₆^- (8-PF₆), and [(TPP)Sb(F)(OH)]⁺ClO₄^- (9- ClO₄). All nine compounds were stable towards atmospheric moisture. X-Ray crystallographic analysis of 6-PF₆ revealed that the antimony atom lies at 0.182 A out-of-plane of the four nitrogens (Δ4N) toward the carbon atom; 6- PF₆: space group P2₁/n, a = 25.49(2), b = 11.27(1), c = 16.58(1) A, β = 96.74(5)°, R = 0.064.