Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/71128
標題: Salicylate exchange in meso-tetraphenylporphyrinato salicylato thallium(III), Tl(tpp) (2-OH-C6H4CO2) and C-13 NMR investigation of its homolog thiocyanato (meso-tetra-p-tolyl-porphyrinato)thallium(III), Tl(tptp)(SCN)
作者: Lu, Y.Y.
Tung, J.Y.
Chen, J.H.
Liao, F.L.
Wang, S.L.
Wang, S.S.
Hwang, L.P.
關鍵字: crystal structure;thallium porphyrin complexes;cis geometries;salicyato ligand;low temperature C-13 NMR analysis;ligand exchange;molecular-structure;cyanide;acetate
Project: Polyhedron
期刊/報告no:: Polyhedron, Volume 18, Issue 1-2, Page(s) 145-150.
摘要: 
This work determines the crystal structure of meso-tetraphenylporphyrinato salicylato thallium(III), Tl(tpp) (2-OH-C6H4CO2)(or Tl(tpp)(SA)). The coordination sphere of the Tl3+ ion is an approximately square-based pyramid in which a chelating bidentate 2OH-C6H4CO2- group occupies the apical site. The average Tl(1)-N bond distance is 2.221 Angstrom and the Tl atom is displaced 0.76 Angstrom from the porphyrin plane. The Tl(1)-O(1) and Tl(1)-O(2) distance are 2.36(1) and 2.47(1) Angstrom, respectively. Variable temperature C-13 NMR measurements reveal that the salicylato group of Tl(tpp)(SA) in CD2Cl2 solvent undergoes a ligand exchange. In the slow exchange region, the carbonyl and C-1" carbons of the salicylato group are separately located at 169.6 ppm [with a (2)J(Tl-C-13) coupling constant of 157 Hz] and 111.5 ppm [with a (3)J(Tl-C-13) coupling constant of 180 Hz] for Tl(tpp)(SA) in CD2Cl2 at -90 degrees C. In the fast exchange region, the C*O and C-1" carbons of the 2-OH-C6H4CO2- ligand in CD2Cl2 at 24 degrees C are singlets at 169.8 and 112.5 ppm, respectively. The C-13 resonance of the axial isocyanato ligand in the compound thiocyanato (meso-tetra-p-tolyl-porphyrinato)thallium(III), Tl(tptp)(SCN), was observed at 110.7 ppm (24 degrees C) with (2)J(Tl-C-13) coupling constant 253 Hz. This finding suggests that thiocyanato group is, as thiocyanate type, axially coordinated to the Tl atom in Tl(tptp)(SCN). In addition, there is no SCN- exchange in the same compound. (C) 1998 Elsevier Science Ltd. All rights reserved.
URI: http://hdl.handle.net/11455/71128
ISSN: 0277-5387
DOI: 10.1016/s0277-5387(98)00277-0
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