100506-72-7Relevant academic research and scientific papers
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.
Acid–Base Properties of Polyhalogenated Tetraphenylporphyrins
Chizhova, N. V.,Ivanova, Yu. B.,Mamardashvili, N. Zh.,Rusanov, A. I.,Shumilova, I. A.
, p. 1054 - 1061 (2020/07/25)
Abstract: [2,3,7,8,12,13,17,18-Octabromo-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II)and[2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II)were synthesized by halogenation of[5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]zinc(II) with N-bromosuccinimide and N-chlorosuccinimide, respectively, in a mixture of chloroformwith methanol. Treatment of the halogenated zinc porphyrins with trifluoroaceticacid in chloroform gave the corresponding free ligands. The isolated compoundswere identified by electronic absorption, 1H NMR, andmass spectra. The acid–base properties of5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin,2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin,and2,3,7,8,12,13,17,18-octachloro-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinwere studied in acetonitrile at 298 K. Their acidity and basicity constants andconcentration ranges of their ionized forms were determined.
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
Heavy-atom effects on metalloporphyrins and polyhalogenated porphyrins
Azenha, Emília G.,Serra, Arménio C.,Pineiro, Marta,Pereira, Mariette M.,Seixas de Melo,Arnaut, Luis G.,Formosinho, Sebasti?o J.,Rocha Gonsalves
, p. 177 - 190 (2008/10/08)
The photophysics of halogenated and metallated tetrakisphenylporphyrins is investigated using single-photon counting, photoacoustic calorimetry and luminescence techniques. The radiationless transition rates in these and related molecules are interpreted with a quantum-mechanical tunnelling model modified to include the effect of spin-orbit coupling in the intersystem crossing rates. It is shown that tetrakisphenylporphyrins with halogens in the ortho positions have long-lived triplet states that are formed in high yields.
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.
Isolation and Characterization of the Principal Kinetic Product in the Preparation of a Sterically Hindered Tetra-arylphorphyrin: X-Ray Structure of a Bis(dipyrromethene) Complex of Zinc, ZnII(C22H13Cl4N2)2*toluene
Hill, Craig L.,Williamson, Michael M.
, p. 1228 - 1229 (2007/10/02)
The principal kinetic product in the Rothemund template synthesis of sterically hindered tetra-arylphorphyrins is not the metalloporphyrin complex but the bis(dipyrromethene) complex; the latter has been isolated from a typical porphyrin preparation, that of tetrakis(2,6-dichlorophenyl)porphyrin, and characterized by u.v.-visible, i.r., and n.m.r. spectroscopy, and X-ray crystallography.
