[Azo-Hyd] Tautomerism and Structure of Selected Metal Complex Dyes AM1 and ZINDO/1 Methods  

作　　者：Krzysztof Wojciechowski Lucjan Szuster Krzysztof Wojciechowski;Lucjan Szuster(Institute of Environmental Engineering and Building Installations, Technical University of Lódź, Lódź, Poland;Leather Research Institute, Lódź, Poland)

机构地区：[1]Institute of Environmental Engineering and Building Installations, Technical University of Lód&zacute , Lód&zacute , Poland [2]Leather Research Institute, Lód&zacute , Poland

出　　处：《Computational Chemistry》2016年第4期97-118,共22页计算化学（英文）

摘　　要：Quantum-chemical calculation methods have been used to examine an influence of tautomeric equilibrium [Azo  Hydrazo] on a structure of 1:2 chromium metal complex dyes called Gryfalan Navy Blue RL (CI 15 707, Acid Blue 193) and Gryfalan Black RL (Acid Black 194). Chromatographic analysis indicates that synthesis yields a mixture of several dyes with different shades. Studies conducted to date have suggested that such dye complexes can constitute Drew-Pfitzner or Pfeiffer-Schetty structural isomers [1]. It is a know fact, that o-hydroxy-azo dyes exist in equilibrium of tautomeric azo and hydrazone forms. We decided to examine, whether color properties of examined metal-complex dyes can be influenced also by an azo-hydrazone equilibrium and what kind of influence on it has sulphonic groups present in molecules. Calculation and optimization of the geometrical structure were performed using the AM1 methods for monoazoo-hydroxy-azo dyesand ZINDO/1 for 1:2 chromium metal complex dyes. It was stated that monoazo dyes can create complexes in both forms: azo and hydrazone, because energy differences between each form of the metal complex dye are so small, that the monoazo dye can, in practice, create complexes in both the azo and the hydrazone form, with energy differences not exceeding about 4 - 11 kcal/mol. It is calculated that spatial structure changes with an angle of about 90° between two molecules of the dye, and angles of 10° - 20° between the naphthalene moieties. Similar electron density on the hydroxyl and ketone groups suggests that the mixture contains a dominant share of the azo form. The presence of an ionised sulphonic group was also found to affect on the tautomer equilibrium.Quantum-chemical calculation methods have been used to examine an influence of tautomeric equilibrium [Azo  Hydrazo] on a structure of 1:2 chromium metal complex dyes called Gryfalan Navy Blue RL (CI 15 707, Acid Blue 193) and Gryfalan Black RL (Acid Black 194). Chromatographic analysis indicates that synthesis yields a mixture of several dyes with different shades. Studies conducted to date have suggested that such dye complexes can constitute Drew-Pfitzner or Pfeiffer-Schetty structural isomers [1]. It is a know fact, that o-hydroxy-azo dyes exist in equilibrium of tautomeric azo and hydrazone forms. We decided to examine, whether color properties of examined metal-complex dyes can be influenced also by an azo-hydrazone equilibrium and what kind of influence on it has sulphonic groups present in molecules. Calculation and optimization of the geometrical structure were performed using the AM1 methods for monoazoo-hydroxy-azo dyesand ZINDO/1 for 1:2 chromium metal complex dyes. It was stated that monoazo dyes can create complexes in both forms: azo and hydrazone, because energy differences between each form of the metal complex dye are so small, that the monoazo dye can, in practice, create complexes in both the azo and the hydrazone form, with energy differences not exceeding about 4 - 11 kcal/mol. It is calculated that spatial structure changes with an angle of about 90° between two molecules of the dye, and angles of 10° - 20° between the naphthalene moieties. Similar electron density on the hydroxyl and ketone groups suggests that the mixture contains a dominant share of the azo form. The presence of an ionised sulphonic group was also found to affect on the tautomer equilibrium.

关 键 词：Acid Dyes Cr Metal Complexes Quantum-Chemical Calculations AM1 and ZINDO/1 Methods 

分 类 号：O62[理学—有机化学]