Metal complexes of meso-tetra-(p-chlorophenyl)porphyrin and meso-tetra-(p-bromophenyl)porphyrin: Tl[(p-Cl)4tpp](OAc) and In[(p-X)4tpp](OAc) [X=Cl, Br, tpp=5,10,15,20-tetraphenylporphyrinate]

Add time:08/22/2019    Source:sciencedirect.com

The crystal structures of acetato-[meso-tetra(p-chlorophenyl)porphyrinato]thallium(III) Tl[(p-Cl)4tpp](OAc) (1), acetato-[meso-tetra(p-chlorophenyl)porphyrinato]indium(III) In[(p-Cl)4tpp](OAc) (2) and acetato-[meso-tetra(p-bromophenyl)porphyrinato]indium(III) In[(p-Br)4tpp](OAc) (3) were determined. The coordination sphere around the Tl3+ ion in 1 is described as six-coordinate distorted square-based pyramid in which the apical site is occupied by a chelating bidentate OAc− group, whereas for the In3+ ion in 2 and 3, it is a five-coordinate regular square-based pyramid in which the unidentate OAc− ligand occupies the axial site. The plane of the four pyrrole nitrogen atoms [i.e. N(1)N(4)] strongly bonded to Tl3+ (or In3+) is adopted as a reference plane 4N. The Tl3+ is moderately out of the 4N plane; its displacement of 0.69 Å is in the same direction as that of the acetate oxygen for 1. The In3+ are located at 0.57 Å from its 4N plane for 2 and 3. The free energy of activation at the coalescence temperature Tc for the intermolecular acetate exchange for 1 in CD2Cl2 is found to be ΔG≠200=42.54 kJ mol−1 whereas the intermolecular OAc− exchange for acetato-[meso-tetra(p-bromophenyl)porphyrinato]thallium(III) Tl[(p-Br)4tpp](OAc) (4) in CD2Cl2 is determined to be ΔG≠200=42.46 kJ mol−1 through 1H NMR temperature-dependent measurements. Moreover, the two oxygen atoms of the acetato group for 2 and 3 are asymmetrically and chelating bidentately bound to the indium atom in CD2Cl2 (or CDCl3) solvent.

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