100506-72-7Relevant articles and documents
Metal Exchange Reactions of o,o′-Dihalosubstituted Cd(II) Tetraphenylporphyrinates with d-Metal Salts in DMF
Chizhova, N. V.,Mamardashvili, N. Z.,Zvezdina, S. V.
, p. 1526 - 1532 (2021/09/11)
Abstract: The metal exchange reactions of Cd(II)-5,10,15,20-tetra(2,6-dichlorophenyl) porphyrin and Cd(II)5,10,15,20-tetra(2,6-difluorophenyl) porphyrin with Zn(II) and Co(II) cations in dimethylformamide were studied by the spectrophotometric method. The kinetic parameters of the metal exchange reaction were calculated and a possible stoichiometric mechanism of the process is proposed. The metal exchange reactions of 2,6-dihalogenated cadmium porphyrins with Zn(II) and Co(II) chlorides and acetates in dimethylformamide were investigated by the sampling method. Zn(II)- and Co(II)-complexes with 5,10,15,20-tetra(2,6-dichlorophenyl)porphyrin and 5,10,15,20-tetra(2,6-difluorophenyl) pophirin were synthesized and identified by UV-Vis, 1H NMR spectroscopy and mass spectrometry methods.
Synthesis and Spectral and Coordination Properties of Perhalogenated Tetraphenylporphyrins
Ivanova, Yu. B.,Chizhova,Mamardashvili, N. Zh.
, p. 2098 - 2104 (2020/12/25)
Abstract: The reaction of [5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) with N-halosuccinimides in chloroform–methanol, chloroform–butan-1-ol, or DMF gave [2,3,7,8,12,13,17,18- octachloro(bromo)-5,10,15,20-tetrakis(2,6-dichlorophenyl)porph
Isolation and characterization of the principal kinetic products in the Rothemund synthesis of sterically hindered tetraarylporphyrins. Crystal and molecular structures of [tetrakis(2,6-dichlorophenyl)porphinato]zinc(II) and bis[(meso-2,6-dichlorophenyl)-5-(o,o′-dichlorobenzyl)dipyrromethene] zinc(II) complexes
Williamson, Michael M.,Prosser-McCartha, Christina M.,Mukundan Jr., Srinivasan,Hill, Craig L.
, p. 1061 - 1068 (2008/10/08)
The Rothemund condensation reaction, the most useful route to hindered 5,10,15,20-tetraarylporphyrins, has been examined in detail in context with the production of tetrakis(2,6-dichlorophenyl)porphyrin, TDCPP, a porphyrin used extensively at present in homogeneous oxygenation and biomimetic heme studies. The principal products from the reaction of pyrrole, 2,6-dichlorobenzaldehyde, and zinc acetate in refluxing 2,4,6-collidine are the bis(dipyrromethene) complex bis[(meso-2,6-dichlorophenyl)-5-(o,o′-dichlorobenzyl)dipyrromethene] zinc(II) (2), produced in ca. 40% yield, and the Zn porphyrin [tetrakis(2,6-dichlorophenyl)porphinato]zinc(II), ZnIITDCPP (1), produced in ca. 10% yield. In contrast to a previous report, there is no evidence that meso,5,5′-trisubstituted dipyrromethenes are formed. Furthermore, no zinc complexes of pyrromethenes nor dipyrromethanes build up to observable levels under the conditions of this aerobic high-temperature condensation reaction. The X-ray crystal structure of 2 coupled with 1H NMR, 13C NMR, infrared, UV-visible, and mass spectral data confirms the formulation of the compound as a Zn2+ ion coordinated by two planar bidentate disubstituted dipyrromethene ligands. Although the data indicate that carbon-carbon bond formation and cyclization in 2 to form the metalloporphyrin, 1, should not be a difficult process, 2 does not produce 1 in appreciable yield under the Rothemund conditions examined in this work. The metalloporphyrin, 1, isolated from the reaction, crystallizes as its five-coordinate N-methylpyrrolidinone (NMP) complex in triclinic space group P1: a = 11.470 (9) ?, b = 13.155 (7) ?, c = 19.894 (10) ?, α = 84.25 (4)°, β = 79.00 (5)°, γ = 75.59 (6)°; V = 2849.3 (3.3) ?3, Z = 2. The zwitterionic canonical form of the O-bound axial NMP is considerably enhanced upon ligation to the zinc, and the pocket depth defined by the eight phenyl o-chloro substituents in 1 is ca. 2.6 ?. Although the spectroscopic data indicate that free-radical bromination of 2 followed by treatment of the product under Rothemund condensation conditions yields some porphyrin, the principal products are brominated derivatives of 1 and 2.
