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標題: Metal complexes of 21-(4-tert-butyl-benzenesulfonamido)-5,10,15, 20-tetraphenyl-porphyrin: Ga(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(OH), Tl(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(O2CCF3) and Zn(N-p-(NSO2C6H4Bu)-Bu-t-tpp) tpp=5,10,15,20-tetraphenylporphyrinate
作者: Shil, W.Z.
Cho, K.Y.
Cheng, C.W.
Chen, J.H.
Wang, S.S.
Liao, F.L.
Tung, J.Y.
Hsieh, H.Y.
Elango, S.
關鍵字: thallium;X-ray diffraction;gallium;dynamic NMR;TFA ligands;molecular-structure;crystal
Project: Polyhedron
期刊/報告no:: Polyhedron, Volume 25, Issue 8, Page(s) 1864-1872.
The crystal structures of trans-hydroxo-N-p-tert-butylbenzenesulfonylimido-meso-tetraphenylporphyrinatogallium(III) 0.5 aqua and 0.5 methanol solvate [Ga(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(OH) center dot 0.5MeOH center dot 0.5H(2)O; 2 center dot 0.5MeOH center dot 0.5H(2)O], cis-trifluoroacetato-N-p-tert-butylbenzenesulfonylimido-meso-tetraphenylporphyrinatothallium(III) [Tl(N-p-(NSO2C6H4Bu)-Bu-t-tpp)(O2CCF3); 3] and N-p-tert-butylbenzenesulfonylimido-meso-tetraphenylporphyrinatozinc(II) 0.7 methanol solvate [Zn(N-p-(NSO2C6H4Bu)-Bu-t-tpp) center dot 0.7MeOH; 4 center dot 0.7MeOH], were determined. The coordination sphere around Tl3+ ion in 3 is a distorted square-based pyramid in which the apical site is occupied by a chelating bidentate CF3CO2- group, whereas for the Ga3+ 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 Zn2+ 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 CD2Cl2 is found to be Delta G(223)(double dagger) = 46.3 kJ/mol through F-19 NMR variable temperature measurements. In the slow-exchange region, the CF3 and carbonyl (CO) carbons of the CF3CO2- group of 3 in CD(2)C(l)2 are separately located at 6 115.9 [(3)J(Tl-C-13) = 155 Hz] and 160.2 [(2)J(Tl-C-13) = 81 Hz] at -90 degrees C. (C) 2005 Elsevier Ltd. All rights reserved.
ISSN: 0277-5387
DOI: 10.1016/j.poly.2005.12.006
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