Ü. Özdemir, N. Karacan, O. Şentürk, S. Sert, Fadime Uğur (Sarikahya)
Abstract Ten new complexes, [M(CO)5(amsh)] [M = Cr; (1a), Mo; (2a), W; (3a)], [Re(CO)4Br(amsh)] (4a), and [Mn(CO)2(amsh)Cp] (5a) and [M(CO)5(msh)] [M = Cr; (1b); Mo, (2b); W, (3b)], [Re(CO)4Br(msh)], (4b), and [Mn(CO)3(msh)], (5b), have been synthesized by the photochemical reaction of the metal carbonyls [M(CO)6] (M = Cr, Mo, and W), [Re(CO)5Br], and [Mn(CO)3Cp] with acetonemethanesulfonylhydrazone (amsh) and methanesulfonyl hydrazine (msh). The complexes have been characterized by elemental analyses, mass spectrometry, FT‐IR and 1H NMR spectroscopy. The spectroscopic studies show that amsh and msh behave as a monodentate ligands coordinating via an imine N donor atom in (1a)–(5a) and a hydrazine N donor atom in (1b)–(5b).
{"title":"Synthesis and Characterization of Metal Carbonyl Complexes of M(CO)6 (M = Cr, Mo, and W), Re(CO)5Br, and Mn(CO)3Cp with Acetonemethanesulfonylhydrazone (amsh) and Methanesulfonylhydrazone (msh)","authors":"Ü. Özdemir, N. Karacan, O. Şentürk, S. Sert, Fadime Uğur (Sarikahya)","doi":"10.1081/SIM-120037527","DOIUrl":"https://doi.org/10.1081/SIM-120037527","url":null,"abstract":"Abstract Ten new complexes, [M(CO)5(amsh)] [M = Cr; (1a), Mo; (2a), W; (3a)], [Re(CO)4Br(amsh)] (4a), and [Mn(CO)2(amsh)Cp] (5a) and [M(CO)5(msh)] [M = Cr; (1b); Mo, (2b); W, (3b)], [Re(CO)4Br(msh)], (4b), and [Mn(CO)3(msh)], (5b), have been synthesized by the photochemical reaction of the metal carbonyls [M(CO)6] (M = Cr, Mo, and W), [Re(CO)5Br], and [Mn(CO)3Cp] with acetonemethanesulfonylhydrazone (amsh) and methanesulfonyl hydrazine (msh). The complexes have been characterized by elemental analyses, mass spectrometry, FT‐IR and 1H NMR spectroscopy. The spectroscopic studies show that amsh and msh behave as a monodentate ligands coordinating via an imine N donor atom in (1a)–(5a) and a hydrazine N donor atom in (1b)–(5b).","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90267216","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 Complexes of some Co(II), Ni(II), and Cu(II) tellurites with 1,3‐diaminopropane ligand have been prepared and charaterized on the basis of elemental analyses, conductivity, magnetic moments, and spectral studies. These complexes have the general formula [ML n (H2O) x ]TeO3 · yH2O, where M(II) = Co(II), Ni(II), and Cu(II); L = 1,3‐diaminopropane; n = 3 [for Co(II)] and 2 [for Ni(II) and Cu(II)]; x = 0 [for Co(II) and Cu(II)] and 2 [for Ni(II)]; y = 4, 1 or 6 [for Co(II), Ni(II), and Cu(II) complexes, respectively]. TGA studies have also been carried out to study the patterns of their decomposition. The lattice constants and other cell parameters of the cobalt(II), nickel(II), and copper(II) tellurite complexes have been determined with the help of x‐ray powder diffraction data. The Co(II) and Ni(II) complexes have an orthorhombic unit cell, whereas the Cu(II) complex has a tetragonal unit cell. On the basis of the cell parameters and diffraction data it has been concluded that the Co(II), Ni(II), and Cu(II) complexes have good crystallinity and packing efficiency.
{"title":"Chemical and Structural Studies of Some Transition Metal Tellurite Complexes with 1,3‐Diaminopropane","authors":"C. Gupta, R. Goutam, K. S. Pitre","doi":"10.1081/SIM-120039260","DOIUrl":"https://doi.org/10.1081/SIM-120039260","url":null,"abstract":"Abstract Complexes of some Co(II), Ni(II), and Cu(II) tellurites with 1,3‐diaminopropane ligand have been prepared and charaterized on the basis of elemental analyses, conductivity, magnetic moments, and spectral studies. These complexes have the general formula [ML n (H2O) x ]TeO3 · yH2O, where M(II) = Co(II), Ni(II), and Cu(II); L = 1,3‐diaminopropane; n = 3 [for Co(II)] and 2 [for Ni(II) and Cu(II)]; x = 0 [for Co(II) and Cu(II)] and 2 [for Ni(II)]; y = 4, 1 or 6 [for Co(II), Ni(II), and Cu(II) complexes, respectively]. TGA studies have also been carried out to study the patterns of their decomposition. The lattice constants and other cell parameters of the cobalt(II), nickel(II), and copper(II) tellurite complexes have been determined with the help of x‐ray powder diffraction data. The Co(II) and Ni(II) complexes have an orthorhombic unit cell, whereas the Cu(II) complex has a tetragonal unit cell. On the basis of the cell parameters and diffraction data it has been concluded that the Co(II), Ni(II), and Cu(II) complexes have good crystallinity and packing efficiency.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89742986","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 Octa‐carboxylate phthalocyanine Cu(II) complex, CuPc(COONa)8, and their pyridine substitutes CuPc(COONa)8(L)2 (L = Py, 4‐MePy), have been synthesized and characterized on the basis of elemental analyses, molar conductance, IR, 1H NMR, and electronic spectral studies. A structure is proposed in which one Pc molecule is coordinated to a metal ion in a tetradentate fashion.
{"title":"Synthesis and Characterization of Water‐Soluble Cu(II) Phthalocyanine Complexes","authors":"B. Wang, H.‐Zh. Ma","doi":"10.1081/SIM-120037523","DOIUrl":"https://doi.org/10.1081/SIM-120037523","url":null,"abstract":"Abstract Octa‐carboxylate phthalocyanine Cu(II) complex, CuPc(COONa)8, and their pyridine substitutes CuPc(COONa)8(L)2 (L = Py, 4‐MePy), have been synthesized and characterized on the basis of elemental analyses, molar conductance, IR, 1H NMR, and electronic spectral studies. A structure is proposed in which one Pc molecule is coordinated to a metal ion in a tetradentate fashion.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83336925","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 Compounds of the composition ZrCl3(OC6H4NO2‐p) and ZrCl2(OC6H4NO2‐p)2 have been synthesized from the reaction of ZrCl4 with equimolar and bimolar amounts of the trimethylsilyl derivative of p‐nitrophenol in benzene under reflux. Attempts to isolate the tetrakis derivative, Zr(OC6H4NO2‐p)4, even by heating the components in high‐boiling solvents were unsuccessful. Based upon analytical data, conductance, cryoscopic, IR and 1H NMR studies, dimeric structures with bridging through phenoxo groups have been proposed for these compounds. The thermal decomposition of these complexes is a combination of both exothermic and endothermic processes, as is inferred from TG/DT studies. Reactions of these compounds with nitrogen bases viz., pyridine, 1,10‐phenanthroline and 2,2′‐bipyridyl results in breakdown of the bridged structure and formation of simple addition compounds, which have been assigned octahedral structures.
{"title":"Synthesis and Characterization of para‐Nitrophenoxides of Zirconium(IV)","authors":"S. C. Chaudhry, C. Verma, S. S. Bhatt, N. Sharma","doi":"10.1081/SIM-120037525","DOIUrl":"https://doi.org/10.1081/SIM-120037525","url":null,"abstract":"Abstract Compounds of the composition ZrCl3(OC6H4NO2‐p) and ZrCl2(OC6H4NO2‐p)2 have been synthesized from the reaction of ZrCl4 with equimolar and bimolar amounts of the trimethylsilyl derivative of p‐nitrophenol in benzene under reflux. Attempts to isolate the tetrakis derivative, Zr(OC6H4NO2‐p)4, even by heating the components in high‐boiling solvents were unsuccessful. Based upon analytical data, conductance, cryoscopic, IR and 1H NMR studies, dimeric structures with bridging through phenoxo groups have been proposed for these compounds. The thermal decomposition of these complexes is a combination of both exothermic and endothermic processes, as is inferred from TG/DT studies. Reactions of these compounds with nitrogen bases viz., pyridine, 1,10‐phenanthroline and 2,2′‐bipyridyl results in breakdown of the bridged structure and formation of simple addition compounds, which have been assigned octahedral structures.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88451446","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 synthesis, spectroscopic, magnetic susceptibility, and superoxide dismutase (SOD) activity measurements of the imidazolate‐bridged complexes [(Salgly)Cu‐Im‐Cu(Salgly)]Na, [(Salgly)Cu‐Im‐Ni(Salgly)]Na, and [(Salgly)Cu‐Im‐Zn(Salgly)]Na, where Salgly = salicylideneglycinate, Im = imidazolate ion are described. Related copper(II) mononuclear complexes are also described. A pH‐dependent EPR and UV‐visible study of a 50% aqueous DMSO solution of the binuclear complexes suggest that the complexes are stable in the pH‐range 6.50–10.50. At lower pH, the imidazolate bridge breaks apart with decreasing pH value.
{"title":"Synthesis, Spectroscopy, and SOD Activity of Some Imidazolate‐Bridged Copper(II) Complexes","authors":"R. N. Patel","doi":"10.1081/SIM-120037526","DOIUrl":"https://doi.org/10.1081/SIM-120037526","url":null,"abstract":"Abstract The synthesis, spectroscopic, magnetic susceptibility, and superoxide dismutase (SOD) activity measurements of the imidazolate‐bridged complexes [(Salgly)Cu‐Im‐Cu(Salgly)]Na, [(Salgly)Cu‐Im‐Ni(Salgly)]Na, and [(Salgly)Cu‐Im‐Zn(Salgly)]Na, where Salgly = salicylideneglycinate, Im = imidazolate ion are described. Related copper(II) mononuclear complexes are also described. A pH‐dependent EPR and UV‐visible study of a 50% aqueous DMSO solution of the binuclear complexes suggest that the complexes are stable in the pH‐range 6.50–10.50. At lower pH, the imidazolate bridge breaks apart with decreasing pH value.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73265839","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 Five new rare earth complexes [RE(L)2(H2O)]2Cl2 · 2H2O [RE(III) = La, Pr, Nd, Sm, Eu] have been synthesized with the ligand 5‐aminosalicylic acid. Their properties have been studied on the basis of microanalyses, molar conductance, magnetic susceptibility, IR, UV‐Vis, 1H NMR spectra, and thermal analyses.
{"title":"Synthesis and Characterization of Light Lanthanide Complexes with 5‐Aminosalicylic Acid","authors":"Xiu-ying Zhang, X. Lei, Z. Dai","doi":"10.1081/SIM-120039261","DOIUrl":"https://doi.org/10.1081/SIM-120039261","url":null,"abstract":"Abstract Five new rare earth complexes [RE(L)2(H2O)]2Cl2 · 2H2O [RE(III) = La, Pr, Nd, Sm, Eu] have been synthesized with the ligand 5‐aminosalicylic acid. Their properties have been studied on the basis of microanalyses, molar conductance, magnetic susceptibility, IR, UV‐Vis, 1H NMR spectra, and thermal analyses.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"87318880","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 Heterobinuclear V(IV), Mo(III), U(VI), Mn(II), Co(II), Ni(II), and Cu(II) ion complexes of ortho‐cresolphthalein complexone (o‐CPC) were prepared and characterized. Elemental and thermal analyses as well as IR, electronic, or ESR spectra and magnetic moment determinations were utilized for the investigation of the complexes. Some complexes were also subjected to polarographic and cyclic voltammetric studies. From the data of these investigations, the structural formulae, the mode of bonding, and geometry of the complexes were obtained. Cyclic voltammetry (CV) and DC polarographic studies were utilized to establish the presence of the metal ions.
{"title":"Binuclear Mixed Metal Complexes of V(IV), Mo(III), and U(VI) o‐Cresolphthalein Complexonates with Other Metal Ions","authors":"R. Issa, A. M. Khedr, Amany Tawfik","doi":"10.1081/SIM-120039259","DOIUrl":"https://doi.org/10.1081/SIM-120039259","url":null,"abstract":"Abstract Heterobinuclear V(IV), Mo(III), U(VI), Mn(II), Co(II), Ni(II), and Cu(II) ion complexes of ortho‐cresolphthalein complexone (o‐CPC) were prepared and characterized. Elemental and thermal analyses as well as IR, electronic, or ESR spectra and magnetic moment determinations were utilized for the investigation of the complexes. Some complexes were also subjected to polarographic and cyclic voltammetric studies. From the data of these investigations, the structural formulae, the mode of bonding, and geometry of the complexes were obtained. Cyclic voltammetry (CV) and DC polarographic studies were utilized to establish the presence of the metal ions.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76115908","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 Two new μ‐oxamido‐bridged heterobinuclear complexes have been synthesized and identified as [Cu(dmoxae)Cr(bpy)2](ClO4)3 (1) and [Cu(dmoxae)Fe(bpy)2](ClO4)3 (2), where dmoxae denotes N, N′‐bis[2‐(dimethylamino)ethyl]oxamido dianion and bpy represents 2,2′‐bipyridine. The two complexes have not yet been isolated in crystalline form suitable for x‐ray structure analysis, but based on elemental analyses, IR, ESR and electronic spectra studies, and molar conductivity measurements, the complexes are proposed to have an extended oxamido‐bridged structure consisting of planar copper(II) and octahedral chromium(III) or iron(III) ions. The two heterobinuclear complexes were further characterized by variable‐temperature magnetic susceptibility (4.2–300 K) measurements and the magnetic data have also been used to deduce the indicated heterobinuclear structure. The results derived from the least‐squares fit of the experimental data have confirmed that the adjacent copper(II) and chromium(III) ions in complex (1) are ferromagnetically coupled through the oxamido‐bridge with the exchange integral J (Cu–Cr) = +16.5 cm−1, while intramolecular antiferromagnetic coupling is detected between the copper(II) and iron(III) ions through the oxamido‐bridge in complex (2) with the exchange integral J (Cu–Fe) = −18.9 cm−1, on the basis of the spin‐Hamiltonian operator, Hˆ = − 2J Sˆ Cu Sˆ M (M = Cr and Fe). The influence of electronic‐structural variations of the metal ions on the nature of spin‐exchange interaction between the paramagnetic centers is also discussed.
摘要合成了两个新的μ‐氧胺桥接杂双核配合物，并鉴定为[Cu(dmoxae)Cr(bpy)2](ClO4)3(1)和[Cu(dmoxae)Fe(bpy)2](ClO4)3(2)，其中dmoxae表示N, N′‐双[2‐(二甲氨基)乙基]氧胺二离子，bpy表示2,2′‐联吡啶。这两种配合物尚未以适合x射线结构分析的晶体形式分离出来，但基于元素分析，IR, ESR和电子能谱研究以及摩尔电导率测量，这些配合物被认为具有由平面铜(II)和八面体铬(III)或铁(III)离子组成的扩展氧胺桥接结构。通过变温磁化率(4.2-300 K)测量进一步表征了这两种杂双核配合物，并利用磁数据推断了所指示的杂双核结构。对实验数据进行最小二乘拟合的结果证实，配合物(1)中相邻的铜(II)和铬(III)离子通过oxamido桥发生铁磁耦合，交换积分J (Cu-Cr) = +16.5 cm−1，而配合物(2)中铜(II)和铁(III)离子通过oxamido桥发生反铁磁耦合，交换积分J (Cu-Fe) = - 18.9 cm−1。基于自旋-哈密顿算符，H = - 2J S - Cu S - M (M = Cr和Fe)。本文还讨论了金属离子的电子结构变化对顺磁中心间自旋交换相互作用性质的影响。
{"title":"Synthesis and Magnetic Studies of μ‐Oxamido‐Bridged Cu(II)–Cr(III) and Cu(II)–Fe(III) Heterobinuclear Complexes","authors":"Cui‐Wei Yan, Yan-Tuan Li, Chunyuan Zhu, H. Guan","doi":"10.1081/SIM-120037517","DOIUrl":"https://doi.org/10.1081/SIM-120037517","url":null,"abstract":"Abstract Two new μ‐oxamido‐bridged heterobinuclear complexes have been synthesized and identified as [Cu(dmoxae)Cr(bpy)2](ClO4)3 (1) and [Cu(dmoxae)Fe(bpy)2](ClO4)3 (2), where dmoxae denotes N, N′‐bis[2‐(dimethylamino)ethyl]oxamido dianion and bpy represents 2,2′‐bipyridine. The two complexes have not yet been isolated in crystalline form suitable for x‐ray structure analysis, but based on elemental analyses, IR, ESR and electronic spectra studies, and molar conductivity measurements, the complexes are proposed to have an extended oxamido‐bridged structure consisting of planar copper(II) and octahedral chromium(III) or iron(III) ions. The two heterobinuclear complexes were further characterized by variable‐temperature magnetic susceptibility (4.2–300 K) measurements and the magnetic data have also been used to deduce the indicated heterobinuclear structure. The results derived from the least‐squares fit of the experimental data have confirmed that the adjacent copper(II) and chromium(III) ions in complex (1) are ferromagnetically coupled through the oxamido‐bridge with the exchange integral J (Cu–Cr) = +16.5 cm−1, while intramolecular antiferromagnetic coupling is detected between the copper(II) and iron(III) ions through the oxamido‐bridge in complex (2) with the exchange integral J (Cu–Fe) = −18.9 cm−1, on the basis of the spin‐Hamiltonian operator, Hˆ = − 2J Sˆ Cu Sˆ M (M = Cr and Fe). The influence of electronic‐structural variations of the metal ions on the nature of spin‐exchange interaction between the paramagnetic centers is also discussed.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"73367315","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 Nine new binuclear lanthanide(III) complexes described by the overall formula [Ln2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Er; Me2bpy = 4,4′‐dimethyl‐2,2′‐bipyridine; and CTPHA = 2‐chloroterephthalate dianion), have been synthesized and characterized by elemental analyses, molar conductance measurements, and IR, ESR, and electronic spectra studies. It is proposed that these complexes have CTPHA‐bridged structures consisting of two lanthanide(III) ions. The variable‐temperature magnetic susceptibility (4–300 K) of [Gd2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 was further measured and the magnetic analysis was carried out by means of a least‐square method to fit the observed data with the susceptibility equation derived from the spin Hamiltonian operator, Ĥ = −2J Ŝ 1 Ŝ 2, giving the exchange parameter J = −0.12 cm−1. This result indicates that the operation of a very weak antiferromagnetic spin‐exchange interaction between the adjacent gadolinium(III) and gadolinium(III) ions within the complex.
{"title":"Synthesis, Characterization, and Magnetism of µ‐2‐Chloroterephthalato‐Bridged Binuclear Lanthanide(III) Complexes","authors":"Cui‐Wei Yan, Yan-Tuan Li, Chunyuan Zhu","doi":"10.1081/SIM-120037519","DOIUrl":"https://doi.org/10.1081/SIM-120037519","url":null,"abstract":"Abstract Nine new binuclear lanthanide(III) complexes described by the overall formula [Ln2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 (Ln = Y, La, Nd, Eu, Gd, Tb, Dy, Ho, Er; Me2bpy = 4,4′‐dimethyl‐2,2′‐bipyridine; and CTPHA = 2‐chloroterephthalate dianion), have been synthesized and characterized by elemental analyses, molar conductance measurements, and IR, ESR, and electronic spectra studies. It is proposed that these complexes have CTPHA‐bridged structures consisting of two lanthanide(III) ions. The variable‐temperature magnetic susceptibility (4–300 K) of [Gd2(CTPHA)(Me2bpy)4(ClO4)2](ClO4)2 was further measured and the magnetic analysis was carried out by means of a least‐square method to fit the observed data with the susceptibility equation derived from the spin Hamiltonian operator, Ĥ = −2J Ŝ 1 Ŝ 2, giving the exchange parameter J = −0.12 cm−1. This result indicates that the operation of a very weak antiferromagnetic spin‐exchange interaction between the adjacent gadolinium(III) and gadolinium(III) ions within the complex.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89112286","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 condensation reaction of N‐acetylaniline with 1,3‐diaminopropane in 2:1 mole ratio under reflux condition generates an intermediate species having C˭N bonds. The in situ reaction of the intermediate with HCHO and 1,3‐diaminopropane in the presence of perchloric acid results in an off‐white solid product. Analytical, FAB mass, IR, 1H NMR and electronic spectral data of this solid are consistent with the formation of the dihydroperchlorate salt of an unsymmetrical 32‐membered [N12] macrocycle [L · 2HClO4] via a capping mechanism of the intermediate species. Reactions of [L · 2HClO4] with Group 12 metal salts, MX2, and their precursors, [M(Ph3P)2Cl2], produce bimetallic complexes with the stoichiometries M2LX2(ClO4)2 (M = Zn, Cd or Hg; X = Cl, NO3, or NCS) and M2LCl2(ClO4)2, respectively, with liberation of 2 mol equiv. of the ancillary ligand, Ph3P, from the precursors. Physico‐chemical and spectroscopic data of the complexes confirm encapsulation of two metal ions in the macrocyclic cavity via coordination through nitrogen atoms of the unsymmetrical aza groups and the counter anions occupy apical positions in the octahedral geometry around the metal ions. The thermodynamic first ionic association constant and related parameters have been determined from conductometric studies using the Fuoss and Edelson method and are discussed.
{"title":"Synthesis and Characterization of a Novel 32‐Membered Unsymmetrical Dinucleating [N12] Macrocycle: Preparation of Bimetallic Complexes M2LX2(ClO4)2 (M = Zn, Cd, or Hg; X = Cl, NCS, or NO3)","authors":"Z. A. Siddiqi, Mohammad Mansoob Khan","doi":"10.1081/SIM-120037515","DOIUrl":"https://doi.org/10.1081/SIM-120037515","url":null,"abstract":"Abstract The condensation reaction of N‐acetylaniline with 1,3‐diaminopropane in 2:1 mole ratio under reflux condition generates an intermediate species having C˭N bonds. The in situ reaction of the intermediate with HCHO and 1,3‐diaminopropane in the presence of perchloric acid results in an off‐white solid product. Analytical, FAB mass, IR, 1H NMR and electronic spectral data of this solid are consistent with the formation of the dihydroperchlorate salt of an unsymmetrical 32‐membered [N12] macrocycle [L · 2HClO4] via a capping mechanism of the intermediate species. Reactions of [L · 2HClO4] with Group 12 metal salts, MX2, and their precursors, [M(Ph3P)2Cl2], produce bimetallic complexes with the stoichiometries M2LX2(ClO4)2 (M = Zn, Cd or Hg; X = Cl, NO3, or NCS) and M2LCl2(ClO4)2, respectively, with liberation of 2 mol equiv. of the ancillary ligand, Ph3P, from the precursors. Physico‐chemical and spectroscopic data of the complexes confirm encapsulation of two metal ions in the macrocyclic cavity via coordination through nitrogen atoms of the unsymmetrical aza groups and the counter anions occupy apical positions in the octahedral geometry around the metal ions. The thermodynamic first ionic association constant and related parameters have been determined from conductometric studies using the Fuoss and Edelson method and are discussed.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2004-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83360048","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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