Metal complexes of 21-(4- tert-butyl-benzenesulfonamido)-5,10,15,20-tetraphenyl-porphyrin: Ga( N- p-NSO 2C 6H 4tBu-tpp)(OH), Tl( N- p-NSO 2C 6H 4tBu-tpp)(O 2CCF 3) and Zn( N- p-NSO 2C 6H 4tBu-tpp) [tpp = 5,10,15,20-tetraphenylporphyrinate

Abstract

The crystal structures of trans-hydroxo- N- p- tert-butylbenzenesulfonylimido- meso-tetraphenylporphyrinatogallium(III) 0.5 aqua and 0.5 methanol solvate [Ga( N- p-NSO 2C 6H 4 t Bu-tpp)(OH) · 0.5MeOH · 0.5H 2O; 2 · 0.5MeOH · 0.5H 2O], cis-trifluoroacetato- N- p- tert-butylbenzenesulfonylimido- meso-tetraphenylporphyrinatothallium(III) [Tl( N- p-NSO 2C 6H 4 t Bu-tpp)(O 2CCF 3); 3] and N- p- tert-butylbenzenesulfonylimido- meso-tetraphenylporphyrinatozinc(II) 0.7 methanol solvate [Zn( N- p-NSO 2C 6H 4 t Bu-tpp) · 0.7MeOH; 4 · 0.7MeOH], were determined. The coordination sphere around Tl 3+ ion in 3 is a distorted square-based pyramid in which the apical site is occupied by a chelating bidentate CF 3 CO 2 - group, whereas for the Ga 3+ ion in 2, it is a distorted trigonal bipyramid with N(2), N(4), and O(1) lying in the equatorial plane. The geometry around Zn 2+ in 4 is a distorted square planar. The free energy of activation at the coalescence temperature T c for the intermolecular trifluoroacetate exchange process for 3 in CD 2Cl 2 is found to be Δ G 223 ‡ = 46.3 kJ / mol through 19F NMR variable temperature measurements. In the slow-exchange region, the CF 3 and carbonyl (CO) carbons of the CF 3 CO 2 - group of 3 in CD 2Cl 2 are separately located at δ 115.9 [ 3 J(Tl– 13C) = 155 Hz] and 160.2 [ 2 J(Tl– 13C) = 81 Hz] at −90 °C.