Metal complexes of 21-(4-tert-butyl-benzenesulfonamido)-5,10,15,20-tetraphenyl-porphyrin: Ga(N-p-NSO2C6H4tBu-tpp)(OH), Tl(N-p-NSO2C6H4tBu-tpp)(O2CCF3) and Zn(N-p-NSO2C6H4tBu-tpp) [tpp=5,10,15,20-tetraphenylporphyrinate]

Autor: Kuan-Yu Cho, Feng-Ling Liao, Shanmugam Elango, Jo-Yu Tung, Shin-Shin Wang, Wei-Zhi Shil, Hsi-Ying Hsieh, Jyh-Horung Chen, Ching-Wen Cheng
Rok vydání: 2006
Předmět:
Zdroj: Polyhedron. 25:1864-1872
ISSN: 0277-5387
Popis: The crystal structures of trans-hydroxo-N-p-tert-butylbenzenesulfonylimido-meso-tetraphenylporphyrinatogallium(III) 0.5 aqua and 0.5 methanol solvate [Ga(N-p-NSO2C6H4tBu-tpp)(OH) · 0.5MeOH · 0.5H2O; 2 · 0.5MeOH · 0.5H2O], cis-trifluoroacetato-N-p-tert-butylbenzenesulfonylimido-meso-tetraphenylporphyrinatothallium(III) [Tl(N-p-NSO2C6H4tBu-tpp)(O2CCF3); 3] and N-p-tert-butylbenzenesulfonylimido-meso-tetraphenylporphyrinatozinc(II) 0.7 methanol solvate [Zn(N-p-NSO2C6H4tBu-tpp) · 0.7MeOH; 4 · 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 CF 3 CO 2 - 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 Tc for the intermolecular trifluoroacetate exchange process for 3 in CD2Cl2 is found to be Δ G 223 ‡ = 46.3 kJ / mol through 19F NMR variable temperature measurements. In the slow-exchange region, the CF3 and carbonyl (CO) carbons of the CF 3 CO 2 - group of 3 in CD2Cl2 are separately located at δ 115.9 [3J(Tl–13C) = 155 Hz] and 160.2 [2J(Tl–13C) = 81 Hz] at −90 °C.
Databáze: OpenAIRE
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