scholarly journals STUDY OF CADMIUM OCTA(4-METHOXYPHENYL)PORPHYRINATE IN REACTION OF METAL EXCHANGE WITH TIN CHLORIDE IN DMF

Author(s):  
Svetlana V. Zvezdina ◽  
Natalya.V. Chizhova ◽  
Nugzar Zh. Mamardashvili ◽  
Oskar I. Koifman

Metal-exchange reaction for complexes with macrocyclic ligands refers to a special type of complex coordination interactions. The reaction of metal exchange has founded wide application for the synthesis of complexes of natural and synthetic porphyrins. In the general form, the metal-exchange reaction may be written as follows:MР + M/Xn(Solv)m-n® M/Р + MXn(Solv)m-nwhere МP and M/P are metalloporphyrins, M/Xn(Solv)m-n are metal salts of solvate complexes. Cd-octa(4-methoxyphenyl)porphyrin was obtained by the reaction of octa(4-methoxyphenyl)-porphyrin-ligand with cadmium chloride in the presence of potassium acetate in dime-thylformamide. The obtained compound was identified by the methods of UV-VIS spectroscopy, 1H NMR and mass-spectrometry. The reaction order on the salt and the complex of cadmium in the case of the reactions of the Cd-octa(4-methoxyphenyl)porphyrin metal-exchange with tin chloride in dimethylformamide is equal to 1. Thus, the metal-exchange reaction is bimolecular and its total rate obeys to the second-order kinetic equation. It is suggested that the metal-exchange reaction of Cd-оcta(4-methoxyphenyl)porphyrin with tin chloride in dimethyl-formamide proceeds through a bimolecular associative mechanism.

2014 ◽  
Vol 18 (01n02) ◽  
pp. 169-172 ◽  
Author(s):  
Svetlana V. Zvezdina ◽  
Natalya V. Chizhova ◽  
Nugzar Zh. Mamardashvili

The metal-exchange reaction of Mg ( II )-octaphenyltetraazaporphyrin with CoCl 2 leading to formation of Co ( II )-octaphenyltetraazaporphyrin was studied by the method of UV-vis spectroscopy. The kinetic parameters of the metal-exchange reaction were determined.


2003 ◽  
Vol 5 (3) ◽  
pp. 313-316 ◽  
Author(s):  
Reinhard W. Hoffmann ◽  
Mark Brönstrup ◽  
Michael Müller

1995 ◽  
Vol 50 (4) ◽  
pp. 545-550 ◽  
Author(s):  
Masaaki Tabata ◽  
Masahiro Ide ◽  
Kentaro Kaneko

Thermochromism was observed for an aqueous solution containing zinc(II) and mercury( II) cations and N-p-nitrobenzyl-5,10,15,20-tetrakis(4-sulfonatophenyl)porphyrin anion (NO2Bz(Htpps)4-) in the temperature range 10 to 70 °C. The equilibrium constants and the thermodynamic parameters of Zn(NO2Bztpps)3- and Hg(NO2Bztpps)3- have been determined spectrophotometrically to elucidate the thermochromism at 10, 15, 20, 25 and 30 °C in 0.1 mol dm-3 NaNO3. The protonation and metalation constants of NO2Bz(Htpps)4- are defined as K2 = [H2P][H+]-1[HP]-1, K3 = [H3P][H+]-1[H2P]-1 and KMP = [M P][H+][M2+]-1[HP]-1, where HP and MP denote the free base form of the prophyrin and the metalloporphyrins of zinc(II) and mercury(II), respectively. Charges of the prophyrin and metalloporphyrins are omitted for simplicity. The following values were found: logK2 = 7.75 ±0.02 (25 °C), ΔH°/kJmol-1 = -21.2±0.5 and ΔS°/Jmol-1K-1 = 77±1, logK3 = 2.55±0.02 (25 °C), ΔH°/kJmol-1 = -25±0.8 and ΔS°/Jmol-1K-1 = -35±3 and log KZnP = 0.63±0.03 (25 °C), ΔH°/kJmol-1 = 31.0±0.8 and ΔS°/Jmol-1K-1 = 116±3, logKHgP = 6.22±0.03 (25 °C), ΔH°/kJmol-1 = 4.5±0.7 and ΔS°/Jmol-1K-1 = 134±2. The distribution curve calculated from the thermodynamic parameters sufficiently agrees with the observed metal exchange reaction between the metalloporphyrins.


2018 ◽  
Vol 20 (7) ◽  
pp. 5312-5318 ◽  
Author(s):  
Bei Zhang ◽  
Olga V. Safonova ◽  
Stephan Pollitt ◽  
Giovanni Salassa ◽  
Annelies Sels ◽  
...  

The fast metal exchange reaction between Au38 and AgxAu38−x nanoclusters has been studied by time resolved in situ X-ray absorption spectroscopy.


1984 ◽  
Vol 57 (8) ◽  
pp. 2319-2320 ◽  
Author(s):  
Toshio Sugita ◽  
Yo-ichi Sakabe ◽  
Toshiaki Sasahara ◽  
Mitsunori Tsukada ◽  
Katsuhiko Ichikawa

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