{"title":"2 -(5 -乙酰氨基- 2 -羟基苯基偶氮)-苯甲酸过渡金属螯合物的合成、红外、磁性、固体反射率和热表征","authors":"G. Mohamed, Z. Zaki","doi":"10.1081/SIM-200026299","DOIUrl":null,"url":null,"abstract":"Abstract The azo ligand 2‐(5‐acetylamino‐2‐hydroxyphenylazo)benzoic acid (H2L) is derived from the diazotization of 4‐acetamidophenol with anthranilic acid. Metal(II) and (III) chelates were prepared and characterized by elemental and thermal analyses, conductance, IR, mass, magnetic, and diffuse reflectance spectra. The complexes were found to have the formulae [Cr(HL)2]Cl · H2O; [Cd(HL)2] · 2H2O; [M(HL)(H2O) z ]X · nH2O for M = Co(II) (X = Cl, z = 1, n = 2), M = Ni(II) (X = Cl, z = 1, n = 2.5); M = Cu(II) (X = AcO, z = 2, n = 2), and M = Zn(II) (X = AcO, z = 1, n = 2); and [Fe(HL)Cl2(H2O)] · 2H2O. The molar conductance data reveal that the Cd(II) and Fe(III) chelates are non‐electrolytes, while the Cr(III), Co(II), Ni(II), Cu(II), and Zn(II) chelates are 1:1 electrolytes. IR spectra show that the ligand is coordinated to the metal ions in a terdentate manner with ONO donor sites of the phenolic OH, azo–N, and carboxylic OH. Magnetic and solid reflectance spectra were used to infer the coordinating capacity of the ligand and the geometrical structure of these complexes. The mass spectra give the possible molecular ion fragments resulting from the fragmentation of the chelates. The thermal behavior of these chelates shows that water molecules (coordinated and uncoordinated) and anions are removed in two successive steps followed immediately by decomposition of the ligand molecule in the subsequent steps. The relative thermal stability of the anhydrous chelates is evaluated. The final decomposition products are found to be the corresponding metal oxides. The thermodynamic activation parameters, such as, E*, ΔH*, ΔS*, and ΔG* are calculated from the TG curves and discussed.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"50 1","pages":"1497 - 1516"},"PeriodicalIF":0.0000,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"12","resultStr":"{\"title\":\"Synthesis, IR, Magnetic, Solid Reflectance, and Thermal Characterization of Transition Metal Chelates with 2‐(5‐Acetylamino‐2‐hydroxyphenylazo)‐benzoic Acid\",\"authors\":\"G. Mohamed, Z. Zaki\",\"doi\":\"10.1081/SIM-200026299\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"Abstract The azo ligand 2‐(5‐acetylamino‐2‐hydroxyphenylazo)benzoic acid (H2L) is derived from the diazotization of 4‐acetamidophenol with anthranilic acid. Metal(II) and (III) chelates were prepared and characterized by elemental and thermal analyses, conductance, IR, mass, magnetic, and diffuse reflectance spectra. The complexes were found to have the formulae [Cr(HL)2]Cl · H2O; [Cd(HL)2] · 2H2O; [M(HL)(H2O) z ]X · nH2O for M = Co(II) (X = Cl, z = 1, n = 2), M = Ni(II) (X = Cl, z = 1, n = 2.5); M = Cu(II) (X = AcO, z = 2, n = 2), and M = Zn(II) (X = AcO, z = 1, n = 2); and [Fe(HL)Cl2(H2O)] · 2H2O. The molar conductance data reveal that the Cd(II) and Fe(III) chelates are non‐electrolytes, while the Cr(III), Co(II), Ni(II), Cu(II), and Zn(II) chelates are 1:1 electrolytes. IR spectra show that the ligand is coordinated to the metal ions in a terdentate manner with ONO donor sites of the phenolic OH, azo–N, and carboxylic OH. Magnetic and solid reflectance spectra were used to infer the coordinating capacity of the ligand and the geometrical structure of these complexes. The mass spectra give the possible molecular ion fragments resulting from the fragmentation of the chelates. The thermal behavior of these chelates shows that water molecules (coordinated and uncoordinated) and anions are removed in two successive steps followed immediately by decomposition of the ligand molecule in the subsequent steps. The relative thermal stability of the anhydrous chelates is evaluated. The final decomposition products are found to be the corresponding metal oxides. The thermodynamic activation parameters, such as, E*, ΔH*, ΔS*, and ΔG* are calculated from the TG curves and discussed.\",\"PeriodicalId\":22160,\"journal\":{\"name\":\"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry\",\"volume\":\"50 1\",\"pages\":\"1497 - 1516\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2004-09-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"12\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://doi.org/10.1081/SIM-200026299\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/10.1081/SIM-200026299","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 12
摘要
摘要偶氮配体2 -(5 -乙酰氨基- 2 -羟基苯基偶氮)苯甲酸(H2L)是由4 -乙酰氨基苯酚与邻氨基苯甲酸重氮化而得。制备了金属(II)和(III)螯合物,并通过元素分析和热分析、电导、红外、质量、磁性和漫反射光谱对其进行了表征。发现配合物的分子式为[Cr(HL)2]Cl·H2O;[Cd(HL)2]·2H2O;[M (HL) (H2O) z] X·nH2O M =有限公司(II) (X = Cl, z = 1, n = 2), M =镍(II) (X = Cl, z = 1, n = 2.5);M = Cu(II) (X = AcO, z = 2, n = 2), M = Zn(II) (X = AcO, z = 1, n = 2);和[Fe(HL)Cl2(H2O)]·2H2O。摩尔电导数据表明,Cd(II)和Fe(III)螯合物为非电解质,而Cr(III)、Co(II)、Ni(II)、Cu(II)和Zn(II)螯合物为1:1电解质。红外光谱表明,该配体与金属离子以三齿状配位的方式与酚羟基、偶氮氮和羧基羟基的ONO供体位点配位。利用磁性和固体反射光谱来推测配体的配位能力和这些配合物的几何结构。质谱给出了可能由螯合物断裂产生的分子离子碎片。这些螯合物的热行为表明,水分子(配位和非配位)和阴离子在两个连续的步骤中被去除,然后在随后的步骤中立即分解配体分子。评价了无水螯合物的相对热稳定性。最终的分解产物是相应的金属氧化物。根据热重曲线计算了E*、ΔH*、ΔS*、ΔG*等热力学活化参数,并对其进行了讨论。
Synthesis, IR, Magnetic, Solid Reflectance, and Thermal Characterization of Transition Metal Chelates with 2‐(5‐Acetylamino‐2‐hydroxyphenylazo)‐benzoic Acid
Abstract The azo ligand 2‐(5‐acetylamino‐2‐hydroxyphenylazo)benzoic acid (H2L) is derived from the diazotization of 4‐acetamidophenol with anthranilic acid. Metal(II) and (III) chelates were prepared and characterized by elemental and thermal analyses, conductance, IR, mass, magnetic, and diffuse reflectance spectra. The complexes were found to have the formulae [Cr(HL)2]Cl · H2O; [Cd(HL)2] · 2H2O; [M(HL)(H2O) z ]X · nH2O for M = Co(II) (X = Cl, z = 1, n = 2), M = Ni(II) (X = Cl, z = 1, n = 2.5); M = Cu(II) (X = AcO, z = 2, n = 2), and M = Zn(II) (X = AcO, z = 1, n = 2); and [Fe(HL)Cl2(H2O)] · 2H2O. The molar conductance data reveal that the Cd(II) and Fe(III) chelates are non‐electrolytes, while the Cr(III), Co(II), Ni(II), Cu(II), and Zn(II) chelates are 1:1 electrolytes. IR spectra show that the ligand is coordinated to the metal ions in a terdentate manner with ONO donor sites of the phenolic OH, azo–N, and carboxylic OH. Magnetic and solid reflectance spectra were used to infer the coordinating capacity of the ligand and the geometrical structure of these complexes. The mass spectra give the possible molecular ion fragments resulting from the fragmentation of the chelates. The thermal behavior of these chelates shows that water molecules (coordinated and uncoordinated) and anions are removed in two successive steps followed immediately by decomposition of the ligand molecule in the subsequent steps. The relative thermal stability of the anhydrous chelates is evaluated. The final decomposition products are found to be the corresponding metal oxides. The thermodynamic activation parameters, such as, E*, ΔH*, ΔS*, and ΔG* are calculated from the TG curves and discussed.