Abstract Schiff base type mononuclear complexes of hexaaza[17]paracyclophane [MLX2] [M = Co(II), Ni(II), Cu(II), and Zn(II); X = Cl or NO3] have been synthesized by the template condensation reaction of terephthalaldehyde, diethylenetriamine, and formaldehyde in 1:1:2:1 molar ratio in methanol. The FT‐IR, 1H NMR, and 13C NMR data indicate that not all of the nitrogen atoms of the macrocyclic ring are coordinated to the metal centre. The reflectance spectra of the solid complexes were recorded confirming the penta‐coordinated geometry around the metal centre. However, the electronic spectra suggested their octahedral environment due to the presence of strongly coordinating solvent DMSO. The magnetic moment values confirm that all of the macrocyclic complexes are high‐spin.
{"title":"Metal Ion Promoted Synthesis of Hexaaza[17]paracyclophane Derived from Terephthalaldehyde Involving Co(II), Ni(II), Cu(II), and Zn(II) and Their Physico‐chemical Properties","authors":"M. Shakir, Nishat Begum, S. Parveen, Y. Azim","doi":"10.1081/SIM-120035958","DOIUrl":"https://doi.org/10.1081/SIM-120035958","url":null,"abstract":"Abstract Schiff base type mononuclear complexes of hexaaza[17]paracyclophane [MLX2] [M = Co(II), Ni(II), Cu(II), and Zn(II); X = Cl or NO3] have been synthesized by the template condensation reaction of terephthalaldehyde, diethylenetriamine, and formaldehyde in 1:1:2:1 molar ratio in methanol. The FT‐IR, 1H NMR, and 13C NMR data indicate that not all of the nitrogen atoms of the macrocyclic ring are coordinated to the metal centre. The reflectance spectra of the solid complexes were recorded confirming the penta‐coordinated geometry around the metal centre. However, the electronic spectra suggested their octahedral environment due to the presence of strongly coordinating solvent DMSO. The magnetic moment values confirm that all of the macrocyclic complexes are high‐spin.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"23 1","pages":"797 - 808"},"PeriodicalIF":0.0,"publicationDate":"2004-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83422603","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract A new oxovanadium complex of the Schiff base obtained by the condensation of 1,2‐bis(p‐aminophenoxy)ethane with salicylaldehyde was synthesized. The complex has been characterized by elemental analyses, magnetic measurements, UV‐VIS and IR spectra. Stability constants and thermodynamic values for complexation between Cu(NO3)2, Zn(NO3)2 · 6H2O, and VOSO4 · 5H2O salts and the ligand synthesized by the method described in the literature in 80% dioxane–water and pure methanol were determined by conductance measurements. The stability constants (log K e) in 80% dioxane/water decrease in the order Cu(II) > (Zn(II). However, just the opposite behavior has been obtained for these metal complexes with the ligand in methanol (Zn(II) > (Cu(II)). The magnitudes of these ion association constants are related to the nature of solvation of the cation and of the complexed cation. The mobility of the complexes is also dependent, in part, upon solvation effects. Since the mobility of the VO(IV)L complex has been found to be higher than that of VO(IV) ion, assuming that the complex–solvent interaction in the VO(IV)‐L systems is comparatively weak. A major consequence of the complexation is the increase in the molar conductivity of the complex and a corresponding large decrease in κ values. For this reason, it was not obtained any stability constant values for VO(IV)‐L systems in two type of solvents.
摘要采用水杨醛与1,2 -双(对氨基苯氧基)乙烷缩合反应合成了一种新的希夫碱氧钒配合物。通过元素分析、磁性测量、紫外可见光谱和红外光谱对配合物进行了表征。用电导法测定了本文方法合成的Cu(NO3)2、Zn(NO3)2·6H2O和VOSO4·5H2O盐与配体在80%二氧六烷水和纯甲醇中络合的稳定性常数和热力学值。在80%二氧六烷/水溶液中，稳定性常数(log K e)以Cu(II) > Zn(II)的顺序递减。然而，这些金属配合物在甲醇中与配体的反应正好相反(Zn(II) > (Cu(II)))。这些离子缔合常数的大小与阳离子和络合阳离子的溶剂化性质有关。配合物的流动性也部分取决于溶剂化效应。由于VO(IV)L络合物的迁移率高于VO(IV)离子的迁移率，假设VO(IV)‐L体系中的络合物-溶剂相互作用相对较弱。络合的一个主要后果是络合物的摩尔电导率的增加和相应的κ值的大幅下降。因此，在两种类型的溶剂中，没有得到VO(IV)‐L体系的稳定常数值。
{"title":"Synthesis and Characterization of a Novel Oxovanadium(IV) Complex and Conductometric Studies with N,N′‐bis(Salicylidene)‐1,2‐bis‐(p‐aminophenoxy)ethane","authors":"H. Temel, Ü. Çakır, H. İbrahim Uğraş","doi":"10.1081/SIM-120035960","DOIUrl":"https://doi.org/10.1081/SIM-120035960","url":null,"abstract":"Abstract A new oxovanadium complex of the Schiff base obtained by the condensation of 1,2‐bis(p‐aminophenoxy)ethane with salicylaldehyde was synthesized. The complex has been characterized by elemental analyses, magnetic measurements, UV‐VIS and IR spectra. Stability constants and thermodynamic values for complexation between Cu(NO3)2, Zn(NO3)2 · 6H2O, and VOSO4 · 5H2O salts and the ligand synthesized by the method described in the literature in 80% dioxane–water and pure methanol were determined by conductance measurements. The stability constants (log K e) in 80% dioxane/water decrease in the order Cu(II) > (Zn(II). However, just the opposite behavior has been obtained for these metal complexes with the ligand in methanol (Zn(II) > (Cu(II)). The magnitudes of these ion association constants are related to the nature of solvation of the cation and of the complexed cation. The mobility of the complexes is also dependent, in part, upon solvation effects. Since the mobility of the VO(IV)L complex has been found to be higher than that of VO(IV) ion, assuming that the complex–solvent interaction in the VO(IV)‐L systems is comparatively weak. A major consequence of the complexation is the increase in the molar conductivity of the complex and a corresponding large decrease in κ values. For this reason, it was not obtained any stability constant values for VO(IV)‐L systems in two type of solvents.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"28 1","pages":"819 - 831"},"PeriodicalIF":0.0,"publicationDate":"2004-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89445181","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract New mono‐ and bis(crown ether) ligands have been synthesized by the condensation of the appropriate formylbenzo‐15‐crown‐5 [(2) and (4)] with ethanolamine and 1,2‐bis[(4‐aminophenoxy)methyl]benzene (6), respectively. The diamine (6), was prepared by the reaction of 1,2‐bis(bromomethyl)benzene and p‐nitrophenol in the presence of NaOH forming the dinitro compound (5) which is subsequently reduced to compound (6) using hydrazine hydrate and Pd/C. Homonuclear sodium complexes of the mono‐ and bis(crown ether) ligands have been prepared with sodium perchlorate. The UV‐VIS spectra of o‐hydroxycrown ether Schiff bases (7), (8), (7a), and (8a) have been studied in various solvents. The results indicate that bands observed at higher values than 400 nm to be the result of the keto‐amine form of the ligands and complexes. All of the crown ether ligands and their complexes have been characterized by elemental analyses, IR, UV, and NMR spectra.
{"title":"The Synthesis of Some New Mono and bis(Crown Ether)s and Their Sodium Complexes. Tautomerism in o‐Hydroxybenzo‐15‐crown‐5 Schiff Bases as Studied by UV‐VIS Spectrophotometry","authors":"M. Hayvalı, Zeliha Hayvalı","doi":"10.1081/SIM-120035952","DOIUrl":"https://doi.org/10.1081/SIM-120035952","url":null,"abstract":"Abstract New mono‐ and bis(crown ether) ligands have been synthesized by the condensation of the appropriate formylbenzo‐15‐crown‐5 [(2) and (4)] with ethanolamine and 1,2‐bis[(4‐aminophenoxy)methyl]benzene (6), respectively. The diamine (6), was prepared by the reaction of 1,2‐bis(bromomethyl)benzene and p‐nitrophenol in the presence of NaOH forming the dinitro compound (5) which is subsequently reduced to compound (6) using hydrazine hydrate and Pd/C. Homonuclear sodium complexes of the mono‐ and bis(crown ether) ligands have been prepared with sodium perchlorate. The UV‐VIS spectra of o‐hydroxycrown ether Schiff bases (7), (8), (7a), and (8a) have been studied in various solvents. The results indicate that bands observed at higher values than 400 nm to be the result of the keto‐amine form of the ligands and complexes. All of the crown ether ligands and their complexes have been characterized by elemental analyses, IR, UV, and NMR spectra.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"52 1","pages":"713 - 732"},"PeriodicalIF":0.0,"publicationDate":"2004-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90324214","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Three new μ‐iodanilato‐bridged binuclear iron(III) complexes were synthesized and characterized, namely [Fe2(IA)(Me2phen)4](ClO4)4 (1), [Fe2(IA)(Ph2phen)4](ClO4)4 (2), and [Fe2(IA)(Phphen)4]‐(ClO4)4 (3), where IA represents the dianion of iodanilic acid; Me2phen, Ph2phen, and Phphen denotes 2,9‐dimethyl‐1,10‐phenanthroline; 4,7‐diphenyl‐1,10‐phenanthroline or 5‐phenyl‐1,10‐phenanthroline, respectively. Based on elemental analyses, molar conductivity and room‐temperature magnetic moment measurements, IR and electronic spectral studies, it is proposed that these complexes have extended IA‐bridged structures consisting of two iron(III) ions, each in a distorted octahedral environment. The complexes (1) and (2) were further characterized by variable‐temperature (4.2–300 K) magnetic susceptibility measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, Ĥ = −2JŜ 1 Ŝ 2, giving the exchange parameter J = −9.21 cm−1 for (1) and J = −10.85 cm−1 for (2). These results are commensurate with weak antiferromagnetic spin‐exchange interaction between the two iron(III) ions within each molecule. The influence of halogen substituents in the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is preliminarily discussed.
{"title":"Synthesis, Characterization, and Magnetism of Binuclear Iron(III) Complexes with Iodanilato as Bridging Ligand","authors":"Yan-Tuan Li, Cui‐Wei Yan, Chunyuan Zhu","doi":"10.1081/SIM-120035957","DOIUrl":"https://doi.org/10.1081/SIM-120035957","url":null,"abstract":"Abstract Three new μ‐iodanilato‐bridged binuclear iron(III) complexes were synthesized and characterized, namely [Fe2(IA)(Me2phen)4](ClO4)4 (1), [Fe2(IA)(Ph2phen)4](ClO4)4 (2), and [Fe2(IA)(Phphen)4]‐(ClO4)4 (3), where IA represents the dianion of iodanilic acid; Me2phen, Ph2phen, and Phphen denotes 2,9‐dimethyl‐1,10‐phenanthroline; 4,7‐diphenyl‐1,10‐phenanthroline or 5‐phenyl‐1,10‐phenanthroline, respectively. Based on elemental analyses, molar conductivity and room‐temperature magnetic moment measurements, IR and electronic spectral studies, it is proposed that these complexes have extended IA‐bridged structures consisting of two iron(III) ions, each in a distorted octahedral environment. The complexes (1) and (2) were further characterized by variable‐temperature (4.2–300 K) magnetic susceptibility measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, Ĥ = −2JŜ 1 Ŝ 2, giving the exchange parameter J = −9.21 cm−1 for (1) and J = −10.85 cm−1 for (2). These results are commensurate with weak antiferromagnetic spin‐exchange interaction between the two iron(III) ions within each molecule. The influence of halogen substituents in the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is preliminarily discussed.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"3 1","pages":"785 - 796"},"PeriodicalIF":0.0,"publicationDate":"2004-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87811520","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), complexes of the type Na2[M(HL)2(H2O)2] of the ligand 2‐hydroxy‐1‐(1‐hydroxy‐2‐naphthylazo)‐6‐nitronaphthalene‐4‐sulfonic acid sodium salt (Eriochrome Black T, NaH2L), have been synthesized and characterized by various physico‐chemical (elemental analyzes, solubility, electrolytic conductances and magnetic susceptibility measurements) and spectral (UV‐Visible spectra, IR spectra, ESR spectra, and powder x‐ray diffraction) techniques for the structure determination and the antifungal activity was measured against 10 fungi. The data suggest 1:2 (M:L) compositions with octahedral geometries around M(II), except for Cu(II), very significant antifungal activity against Alternaria brassicicola and Alternaria brassicae and moderate activity against the fungi Alternaria solanae, Curvularia species, Curvularia lunata, Helminthosporium oryzae, Collectotrichum capsici, Aspergillus niger, Aspergillus flavus, and Fusarium udum.
摘要:本文合成了配体2‐羟基‐1‐(1‐羟基‐2‐萘偶氮)‐6‐硝基萘‐4‐磺酸钠盐(Eriochrome Black T, NaH2L)的Na2[M(HL)2(H2O)2]型配合物Mn(II)、Fe(II)、Co(II)、Ni(II)、Cu(II)和Zn(II)，并通过各种物理化学(元素分析、溶解度、电导率和磁化率测量)和光谱(UV‐可见光光谱、IR光谱、ESR光谱、NaH2L光谱)对其进行了表征。并用粉末x射线衍射技术对其结构进行了测定，并对10种真菌进行了抑菌活性测定。数据表明，除Cu(II)外，M(II)周围八面体几何形状为1:2 (M:L)的组合物对油菜赤霉和油菜赤霉的抑菌活性非常显著，对茄赤霉、曲霉、月曲霉、米霉、辣椒赤霉、黑曲霉、黄曲霉和镰刀菌的抑菌活性中等。
{"title":"Synthesis, Characterization, Spectral Studies, and Antifungal Activity of Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) Complexes with 2‐Hydroxy‐1‐(1‐hydroxy‐2‐naphthylazo)‐6‐nitronaphthalene‐4‐sulfonic Acid Sodium Salt","authors":"G. Pandey, K. Narang","doi":"10.1081/SIM-120028309","DOIUrl":"https://doi.org/10.1081/SIM-120028309","url":null,"abstract":"Abstract Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II), complexes of the type Na2[M(HL)2(H2O)2] of the ligand 2‐hydroxy‐1‐(1‐hydroxy‐2‐naphthylazo)‐6‐nitronaphthalene‐4‐sulfonic acid sodium salt (Eriochrome Black T, NaH2L), have been synthesized and characterized by various physico‐chemical (elemental analyzes, solubility, electrolytic conductances and magnetic susceptibility measurements) and spectral (UV‐Visible spectra, IR spectra, ESR spectra, and powder x‐ray diffraction) techniques for the structure determination and the antifungal activity was measured against 10 fungi. The data suggest 1:2 (M:L) compositions with octahedral geometries around M(II), except for Cu(II), very significant antifungal activity against Alternaria brassicicola and Alternaria brassicae and moderate activity against the fungi Alternaria solanae, Curvularia species, Curvularia lunata, Helminthosporium oryzae, Collectotrichum capsici, Aspergillus niger, Aspergillus flavus, and Fusarium udum.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"95 1","pages":"397 - 415"},"PeriodicalIF":0.0,"publicationDate":"2004-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75002891","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract 1‐(1H‐Benzotriazol‐1‐acetyl)‐5‐hydroxy‐3‐trifluoromethyl‐5‐(2‐thienyl)‐2‐pyrazoline (H2L) has been synthesized by condensing 1H‐benzotriazol‐1‐acetic acid hydrazide with 1‐(2‐thienyl)‐4,4,4‐trifluoro‐1,3‐butanedione. Complexes of the composition [ML]2 [M = Zn(II), Cu(II), Ni(II)] and [ML(H2O)]2 [M = Co(II)] have been prepared by refluxing the pyrazoline and metal acetate hydrates in ethanol. The ligand and its complexes have been characterized by elemental analyses, IR, 1H NMR, magnetic susceptibility measurements, and thermogravimetric analysis (TGA). The spectra show that the ligand H2L coordinates as tridentate ligand through the enolic oxygens and the nitrogen of the azomethine group. For the complex [ML(H2O)]2, the S atom of the thienyl group also coordinates with the metal.
{"title":"Synthesis of 1‐(1‐H‐Benzotriazolyl‐1‐acetyl)‐5‐hydroxy‐3‐trifluoromethyl‐5‐(2‐thienyl)‐2‐pyrazoline and Its Transition Metal Complexes","authors":"Zenglu Liu","doi":"10.1081/SIM-120030434","DOIUrl":"https://doi.org/10.1081/SIM-120030434","url":null,"abstract":"Abstract 1‐(1H‐Benzotriazol‐1‐acetyl)‐5‐hydroxy‐3‐trifluoromethyl‐5‐(2‐thienyl)‐2‐pyrazoline (H2L) has been synthesized by condensing 1H‐benzotriazol‐1‐acetic acid hydrazide with 1‐(2‐thienyl)‐4,4,4‐trifluoro‐1,3‐butanedione. Complexes of the composition [ML]2 [M = Zn(II), Cu(II), Ni(II)] and [ML(H2O)]2 [M = Co(II)] have been prepared by refluxing the pyrazoline and metal acetate hydrates in ethanol. The ligand and its complexes have been characterized by elemental analyses, IR, 1H NMR, magnetic susceptibility measurements, and thermogravimetric analysis (TGA). The spectra show that the ligand H2L coordinates as tridentate ligand through the enolic oxygens and the nitrogen of the azomethine group. For the complex [ML(H2O)]2, the S atom of the thienyl group also coordinates with the metal.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"PER-7 1","pages":"469 - 478"},"PeriodicalIF":0.0,"publicationDate":"2004-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84585461","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Cu(II), Co(II), Ni(II), and Zn(II) metal complexes of a new SNO tridentate heterocyclic Schiff base derived from the reaction of 1‐amino‐5‐benzoyl‐4‐phenyl‐1H‐pyrimidine‐2‐thione with salicylaldehyde have been synthesized and characterized on the basis of elemental analyses, electronic, IR, and 1H NMR spectra, and also by molar conductivity measurements, magnetic moment measurements and thermogravimetric analyses (TGA). It has been found that the Schiff base behaves as a neutral tridentate SNO ligand forming chelates with 1:2 or 1:1 (metal:ligand) stoichiometry. The complexes of Co(II), Ni(II), and Zn(II) are proposed to have an octahedral structure, while the Cu(II) complex is suggested to have a square–pyramidal geometry. All of the complexes show nonelectrolytic behavior.
{"title":"A New Heterocyclic Schiff Base and Its Metal Complexes","authors":"M. Sönmez, M. Şekerci","doi":"10.1081/SIM-120030436","DOIUrl":"https://doi.org/10.1081/SIM-120030436","url":null,"abstract":"Abstract Cu(II), Co(II), Ni(II), and Zn(II) metal complexes of a new SNO tridentate heterocyclic Schiff base derived from the reaction of 1‐amino‐5‐benzoyl‐4‐phenyl‐1H‐pyrimidine‐2‐thione with salicylaldehyde have been synthesized and characterized on the basis of elemental analyses, electronic, IR, and 1H NMR spectra, and also by molar conductivity measurements, magnetic moment measurements and thermogravimetric analyses (TGA). It has been found that the Schiff base behaves as a neutral tridentate SNO ligand forming chelates with 1:2 or 1:1 (metal:ligand) stoichiometry. The complexes of Co(II), Ni(II), and Zn(II) are proposed to have an octahedral structure, while the Cu(II) complex is suggested to have a square–pyramidal geometry. All of the complexes show nonelectrolytic behavior.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"12 1","pages":"489 - 502"},"PeriodicalIF":0.0,"publicationDate":"2004-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"85443646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract Binary mononuclear complexes of the Schiff base ligand 1,4‐di(hydroxybenzylidene)thiosemicarbazide (H2L) and the transition metal ions Cu(II), Ni(II), Zn(II), and Fe(III) were prepared in the presence of various molar ratios of LiOH. The binary complexes react with 8‐hydroxyquinoline (8‐HOqu) and oxalic acid (H2Ox) to form mixed‐ligand complexes. The mixed ligand complexes were prepared by using various molar ratios of LiOH. The thermal studies explored the stability of the mixed‐ligands in their complexes as the isolated thermal products also contain the mixed ligands. All of the binary and mixed‐ligand complexes have octahedral configurations except [CuHL]Cl and [ZnL], which have square‐planar geometrics. The Schiff base ligand (H2L) is coordinated to the central metal atom as a neutral, monoanionic and/or dianionic tetradentate ONNO ligand in the binary complexes and in the mixed‐ligand complexes. The mixed‐ligand, 8‐HOqu behaves as a neutral or monoanionic bidentate ligand. The oxalato ligand coordinates as a dianionic bidentate or a bridged bidentate ligand towards Fe(III) ions. All complexes and the corresponding thermal products were isolated and their structures were elucidated by elemental analyses, conductance, IR and electronic absorption spectra, magnetic moments, 1H NMR and TG‐DSC measurements as well as by mass spectroscopy. The free ligand H2L and its metal complexes showed higher antibacterial activity than some of the investigated antibiotics, doxycillin, sulperazon, septrin, cefobid, nitrofurantion, and erythromycin.
{"title":"Mixed‐Ligand Complexes of a Schiff Base, 8‐Hydroxyquinoline and Oxalic Acid with Cu(II), Ni(II), Zn(II), and Fe(III) Ions: Pyrolytic Products and Biological Activities","authors":"M. Mashaly, Z. H. Abd-Elwahab, A. Faheim","doi":"10.1081/SIM-120028300","DOIUrl":"https://doi.org/10.1081/SIM-120028300","url":null,"abstract":"Abstract Binary mononuclear complexes of the Schiff base ligand 1,4‐di(hydroxybenzylidene)thiosemicarbazide (H2L) and the transition metal ions Cu(II), Ni(II), Zn(II), and Fe(III) were prepared in the presence of various molar ratios of LiOH. The binary complexes react with 8‐hydroxyquinoline (8‐HOqu) and oxalic acid (H2Ox) to form mixed‐ligand complexes. The mixed ligand complexes were prepared by using various molar ratios of LiOH. The thermal studies explored the stability of the mixed‐ligands in their complexes as the isolated thermal products also contain the mixed ligands. All of the binary and mixed‐ligand complexes have octahedral configurations except [CuHL]Cl and [ZnL], which have square‐planar geometrics. The Schiff base ligand (H2L) is coordinated to the central metal atom as a neutral, monoanionic and/or dianionic tetradentate ONNO ligand in the binary complexes and in the mixed‐ligand complexes. The mixed‐ligand, 8‐HOqu behaves as a neutral or monoanionic bidentate ligand. The oxalato ligand coordinates as a dianionic bidentate or a bridged bidentate ligand towards Fe(III) ions. All complexes and the corresponding thermal products were isolated and their structures were elucidated by elemental analyses, conductance, IR and electronic absorption spectra, magnetic moments, 1H NMR and TG‐DSC measurements as well as by mass spectroscopy. The free ligand H2L and its metal complexes showed higher antibacterial activity than some of the investigated antibiotics, doxycillin, sulperazon, septrin, cefobid, nitrofurantion, and erythromycin.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"9 1","pages":"233 - 268"},"PeriodicalIF":0.0,"publicationDate":"2004-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"91349202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract The new ligands, 1,5,8,12‐tetraaza‐4‐(1′,1′‐dimethylethyl)‐2‐(1″,1″,2″,2″,3″,3″,3″‐heptafluoropropyl)‐9,11‐(dimethyl)‐cyclotetradeca‐1,4,8,11‐tetraene (L1) and 1,5,9,13‐tetraaza‐4‐(1′,1′‐dimethylethyl)‐2‐(1″,1″,2″,2″,3″,3″,3″‐heptafluoropropyl)‐10,12‐(dimethyl)‐cyclohexadeca‐1,4,9,12‐tetraene (L2), have been prepared by the reaction of 1,1,2,2,3,3,3‐heptafluoro‐7,7‐dimethyl‐4,6‐octanedione with ethylenediamine and acetyl acetone (L1) and 1,1,2,2,3,3,3‐heptafluoro‐7,7‐dimethyl‐4,6‐octanedione with 1,3‐diaminopropane and acetylacetone (L2), respectively. Their complexes with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions have also been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, molar conductance measurements, IR, EPR, 1H NMR, and UV‐Visible spectra. The molar conductance values show that the complexes of Fe(III) and Cr(III) are 1:1 electrolytes, the Ni(II) and Cu(II) complexes are 1:2 electrolytes while those of Mn(II), Co(II), and Zn(II) appear to be non‐ionic. An octahedral structure has been proposed for all of these metal ions except for those of Cu(II) and Ni(II), which appear to be square‐planar. The β values indicate a considerable orbital overlap in the metal–ligand bond. All of the compounds have been tested against gram‐positive bacteria of Staphylococcus aureus and gram‐negative bacteria of Escherichia coli. The results show that these compounds inhibit the growth of bacteria.
{"title":"Synthesis and Characterization of New Macrocycles Containing Pendant Groups","authors":"N. Nishat, Rahis‐ud‐din, M. Haq","doi":"10.1081/SIM-120028305","DOIUrl":"https://doi.org/10.1081/SIM-120028305","url":null,"abstract":"Abstract The new ligands, 1,5,8,12‐tetraaza‐4‐(1′,1′‐dimethylethyl)‐2‐(1″,1″,2″,2″,3″,3″,3″‐heptafluoropropyl)‐9,11‐(dimethyl)‐cyclotetradeca‐1,4,8,11‐tetraene (L1) and 1,5,9,13‐tetraaza‐4‐(1′,1′‐dimethylethyl)‐2‐(1″,1″,2″,2″,3″,3″,3″‐heptafluoropropyl)‐10,12‐(dimethyl)‐cyclohexadeca‐1,4,9,12‐tetraene (L2), have been prepared by the reaction of 1,1,2,2,3,3,3‐heptafluoro‐7,7‐dimethyl‐4,6‐octanedione with ethylenediamine and acetyl acetone (L1) and 1,1,2,2,3,3,3‐heptafluoro‐7,7‐dimethyl‐4,6‐octanedione with 1,3‐diaminopropane and acetylacetone (L2), respectively. Their complexes with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions have also been synthesized and characterized by elemental analyses, magnetic susceptibility measurements, molar conductance measurements, IR, EPR, 1H NMR, and UV‐Visible spectra. The molar conductance values show that the complexes of Fe(III) and Cr(III) are 1:1 electrolytes, the Ni(II) and Cu(II) complexes are 1:2 electrolytes while those of Mn(II), Co(II), and Zn(II) appear to be non‐ionic. An octahedral structure has been proposed for all of these metal ions except for those of Cu(II) and Ni(II), which appear to be square‐planar. The β values indicate a considerable orbital overlap in the metal–ligand bond. All of the compounds have been tested against gram‐positive bacteria of Staphylococcus aureus and gram‐negative bacteria of Escherichia coli. The results show that these compounds inhibit the growth of bacteria.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"22 1","pages":"335 - 351"},"PeriodicalIF":0.0,"publicationDate":"2004-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"78480042","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Abstract The novel, unsymmetrical, mixed‐donor, tetradentate amido, and oxo complexes of V(IV) of the general formula VOL x were synthesized by a nontemplate method and characterized by physico‐chemical methods. The ligands were prepared by a two‐stage aldol condensation reaction in the molar ratio 1:1 of 2‐hydroxybenzaldehyde, 2′‐hydroxyacetophenone, or 2′,4′‐dihydroxyacetophenone and 1,2‐diaminopropane of the general formula HA x (x = 1–3) as precursors. The tetradentate mixed donor ligands of the general formula H2L x (x = 1–6) were obtained by condensation reaction of precursors with appropriate ketone or aldehyde. The synthesis of the ligand system, described here, is an efficient and easy method with the advantages of high yield, selectivity, and short reaction times. Only a brown polymeric form was obtained for VOL2 and green monomeric forms were obtained for VOL x , x = 1, 3–5, while in the presence of strong field ligands only monomeric forms were obtained. These observations suggest that monomeric forms of oxovanadium(IV) complexes exhibit a coordination number of five with N2O3 donor sets and the polymeric form exhibits a coordination number of six with N2O4 donor sets. Analytical data, 1H NMR, IR, UV–VIS spectra, and elemental analyses confirm the nature of the products.
摘要采用非模板法合成了通式VOL x中新型的不对称、混合给体、四齿胺和氧配合物，并用物理化学方法对其进行了表征。以2 -羟基苯甲醛、2 ' -羟基苯乙酮或2 '，4 ' -二羟基苯乙酮和1,2 -二氨基丙烷为前体(x = 1 - 3)，以摩尔比为1:1的两级醛醇缩合反应制备配体。通过前驱体与适当的酮或醛缩合反应，得到了通式H2L x (x = 1-6)的四齿混合给体配体。本文所描述的配体体系的合成是一种高效、简便的方法，具有收率高、选择性好、反应时间短等优点。VOL2只得到棕色的聚合物形式，而VOL x, x = 1,3 - 5只得到绿色的单体形式，而在强场配体存在下只得到单体形式。这些观察结果表明，氧化钒(IV)配合物的单体形式与N2O3供体集的配位数为5，聚合物形式与N2O4供体集的配位数为6。分析数据，1H NMR, IR, UV-VIS光谱和元素分析证实了产品的性质。
{"title":"New Unsymmetrical Oxovanadium(IV) Complexes of Mixed‐Donor Amido and Oxo Ligands","authors":"S. Mohebi, D. Boghaei","doi":"10.1081/SIM-120030444","DOIUrl":"https://doi.org/10.1081/SIM-120030444","url":null,"abstract":"Abstract The novel, unsymmetrical, mixed‐donor, tetradentate amido, and oxo complexes of V(IV) of the general formula VOL x were synthesized by a nontemplate method and characterized by physico‐chemical methods. The ligands were prepared by a two‐stage aldol condensation reaction in the molar ratio 1:1 of 2‐hydroxybenzaldehyde, 2′‐hydroxyacetophenone, or 2′,4′‐dihydroxyacetophenone and 1,2‐diaminopropane of the general formula HA x (x = 1–3) as precursors. The tetradentate mixed donor ligands of the general formula H2L x (x = 1–6) were obtained by condensation reaction of precursors with appropriate ketone or aldehyde. The synthesis of the ligand system, described here, is an efficient and easy method with the advantages of high yield, selectivity, and short reaction times. Only a brown polymeric form was obtained for VOL2 and green monomeric forms were obtained for VOL x , x = 1, 3–5, while in the presence of strong field ligands only monomeric forms were obtained. These observations suggest that monomeric forms of oxovanadium(IV) complexes exhibit a coordination number of five with N2O3 donor sets and the polymeric form exhibits a coordination number of six with N2O4 donor sets. Analytical data, 1H NMR, IR, UV–VIS spectra, and elemental analyses confirm the nature of the products.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"133 1","pages":"611 - 626"},"PeriodicalIF":0.0,"publicationDate":"2004-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86475577","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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