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|標題:||Thallium complexes of meso-tetra-(p-chlorophenyl)porphyrin: trifluoroacetato- meso-tetra(p-chlorophenyl) porphyrinato thallium(III) and pentafluoropropionato meso-tetra(p-chlorophenyl)porphyrinato thallium(II I)||作者:||Lee, Y.Y.
|關鍵字:||crystal structures;intermolecular exchange;pentafluoropropionato;complex;thallium meso-tetra-(p-chlorophenyl)porphyrin complexes;crystal-structure;molecular-structures;5,10,15,20-tetraphenylporphyrinate;porphyrins;nmr||Project:||Inorganic Chemistry Communications||期刊/報告no：:||Inorganic Chemistry Communications, Volume 6, Issue 3, Page(s) 252-258.||摘要:||
The crystal structures of trifluoroacetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III), Tl[(p-Cl)(4)tpp](O2CCF3) (1), and pentafluoropropionato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl[(p-Cl)(4)tpp](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)1 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 Angstrom (or 0.59 Angstrom) 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 T-c for the intermolecular trifluoroacetate exchange for 1 in CD2Cl2 is found to be AG(178)(not equal) = 36.6 kJ/mol whereas the intermolecular pentafluoropropionate exchange for 2 in CD2Cl2 is determined to be AG(213)(not equal) = 41.5 kJ/mol through F-19 and C-13 NMR temperature-dependent measurements. (C) 2002 Elsevier Science B.V. All rights reserved.
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