Thallium complexes of meso-tetra-(p-chlorophenyl)porphyrin: trifluoroacetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) and pentafluoropropionato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) |
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| Affiliation: | 1. Department of Chemistry, National Chung-Hsing University, Taichung 402, Taiwan;2. Chung Hwa College of Medical Technology, Tainan 717, Taiwan;3. Department of Chemistry, National Tsing-Hua University, Hsin-Chu 300, Taiwan;4. Tzu Hui Institute of Technology, Ping Tung 92641, Taiwan;5. Shuang Bang Industrial Corporation, Nantou 540, Taiwan;1. Department of Environmental and Life Sciences, Toyohashi University of Technology, Tempaku-cho, Toyohashi 441-8580, Japan;2. Department of Chemistry, University of Dhaka, Dhaka 1000, Bangladesh;3. Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China;4. Graduate School of Biomedical Engineering, Tohoku University, Aoba, Sendai 980-8575, Japan;1. Universite de Paris Est, Institut de Chimie et des Matériaux Paris Est, CNRS-UPEC, UMR7182, 2-8 rue Henri Dunant, 94320 Thiais, France;2. Institute of High Pressure Physics PAS, ul. Sokolowska 29, 01-142 Warsaw, Poland;1. Biomedical Engineering Department, Rutgers University, United States;2. Chemical and Biochemical Engineering Department, Rutgers University, United States;3. Department of Surgery, Rutgers-Robert Wood Johnson Medical School, United States |
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| Abstract: | The crystal structures of trifluoroacetato-meso-tetra(p-chlorophenyl)porphyrinato]thallium(III), Tl(p-Cl)4tpp](O2CCF3) (1), and pentafluoropropionato-meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl(p-Cl)4tpp](O2CCF2CF3) (2), were determined. The coordination sphere around the Tl3+ ion is described as five-coordinate regular square-based pyramid (RSBP) in which the apical site is occupied by an unidentate CF3CO2? ligand for 1 whereas the unidentate CF3CF2CO2? ligand occupies the axial site for 2. The plane of the four pyrrole nitrogen atoms i.e., N(1)–N(4)] strongly bonded to Tl3+ is adopted as a reference plane 4N. The Tl3+ is moderately out of the 4N plane; its displacement of 0.58 Å (or 0.59 Å) for 1 (or 2) is in the same direction as that of the trifluoroacetate oxygen for 1 (or pentafluoropropionate oxygen for 2). The free energy of activation at the coalescence temperature Tc for the intermolecular trifluoroacetate exchange for 1 in CD2Cl2 is found to be ΔG≠178=36.6 kJ/mol whereas the intermolecular pentafluoropropionate exchange for 2 in CD2Cl2 is determined to be ΔG≠213=41.5 kJ/mol through 19F and 13C NMR temperature-dependent measurements. |
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