Sadiq-ur-Rehman, Saqib Ali, A. Badshah, M. Mazhar, Xueqing Song, G. Eng, K. Khan
Abstract In an effort to develop new organotin(IV) compounds of industrial and biological importance, a series of di‐ and triorganotin(IV) complexes of (E)‐3‐(4‐chlorophenyl)‐2‐phenylpropenoic acid with the general formula R4‐n SnL n have been synthesized by the reaction of the corresponding organotin chlorides with the sodium salt of (E)‐3‐(4‐chlorophenyl)‐2‐phenylpropenoic acid (C15H10ClO2Na) where, R = CH3, C2H5, n‐C4H9, C6H5, C6H5 · CH2, n = 1 or 2 and L = acid anion (C15H10ClO2 −). The dimeric tetraorganodicarboxylatodistannoxanes [(Me2SnL)2O]2 compound (2) and [(Bu2SnL)2O]2 compound (4), L = C15H10ClO2 −, were synthesized by the reaction of R2SnO with the ligand acid (HL) in 1:1 molar ratio with azeotropic removal of water. The structures of the complexes are discussed on the basis of IR, multinuclear (1H, 13C, 119Sn) NMR, 119mSn Mössbauer spectroscopies and mass spectrometry. The spectroscopic results substantiate that all the diorganotin(IV) derivatives possess trigonal‐bipyramidal structures in solution and octahedral geometry in the solid state. A linear polymeric trigonal‐bipyramidal structure in the solid state and a tetrahedral environment around the tin atom in non‐coordinating solvents has been proposed for the triorganotin(IV) derivatives. The Δν [Δν = νasym(COO) − νsym(COO)] values obtained from the IR data, in comparison to the ligand acid and its sodium salt, fall in the range which shows that the ligand may act as a bidentate coordinating group through the carboxyl (COO) oxygen atoms. The biological activity and LD50 data of the synthesized compounds are also reported. The triorganotin(IV) complexes exhibit significantly better activities than the diorganotin(IV) derivatives. The LD50 data show that most of the investigated compounds are cytotoxic.
{"title":"Synthesis, Spectroscopic Characterization: (IR, Multinuclear NMR, 119mSn Mössbauer and Mass Spectrometry), and Biological Activity (Antibacterial, Antifungal, and Cytotoxicity) of Di‐ and Triorganotin(IV) Complexes of (E)‐3‐(4‐Chlorophenyl)‐2‐phenylpropenoic Acid","authors":"Sadiq-ur-Rehman, Saqib Ali, A. Badshah, M. Mazhar, Xueqing Song, G. Eng, K. Khan","doi":"10.1081/SIM-200026257","DOIUrl":"https://doi.org/10.1081/SIM-200026257","url":null,"abstract":"Abstract In an effort to develop new organotin(IV) compounds of industrial and biological importance, a series of di‐ and triorganotin(IV) complexes of (E)‐3‐(4‐chlorophenyl)‐2‐phenylpropenoic acid with the general formula R4‐n SnL n have been synthesized by the reaction of the corresponding organotin chlorides with the sodium salt of (E)‐3‐(4‐chlorophenyl)‐2‐phenylpropenoic acid (C15H10ClO2Na) where, R = CH3, C2H5, n‐C4H9, C6H5, C6H5 · CH2, n = 1 or 2 and L = acid anion (C15H10ClO2 −). The dimeric tetraorganodicarboxylatodistannoxanes [(Me2SnL)2O]2 compound (2) and [(Bu2SnL)2O]2 compound (4), L = C15H10ClO2 −, were synthesized by the reaction of R2SnO with the ligand acid (HL) in 1:1 molar ratio with azeotropic removal of water. The structures of the complexes are discussed on the basis of IR, multinuclear (1H, 13C, 119Sn) NMR, 119mSn Mössbauer spectroscopies and mass spectrometry. The spectroscopic results substantiate that all the diorganotin(IV) derivatives possess trigonal‐bipyramidal structures in solution and octahedral geometry in the solid state. A linear polymeric trigonal‐bipyramidal structure in the solid state and a tetrahedral environment around the tin atom in non‐coordinating solvents has been proposed for the triorganotin(IV) derivatives. The Δν [Δν = νasym(COO) − νsym(COO)] values obtained from the IR data, in comparison to the ligand acid and its sodium salt, fall in the range which shows that the ligand may act as a bidentate coordinating group through the carboxyl (COO) oxygen atoms. The biological activity and LD50 data of the synthesized compounds are also reported. The triorganotin(IV) complexes exhibit significantly better activities than the diorganotin(IV) derivatives. The LD50 data show that most of the investigated compounds are cytotoxic.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"2 1","pages":"1379 - 1399"},"PeriodicalIF":0.0,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89697640","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 cobalt(II) β‐ketoamines complexes {Co[CH3C(O)CHC(CH3)NR]2; R = CH3, CH2(OH)CH2, C4H9} and ketoiminates {Co[CH3C(O)CH(CH3)C(‐N(CH2) n N‐)C(CH3)CHC(O)CH3]} and their adducts with 2,2′‐bipyridine (bipy) and 1,10‐phenanthroline (phen) have been synthesized and characterized by elemental analyses, magnetic susceptibility, conductivity, infrared, and electronic spectral measurements. The ligands coordinate to the cobalt ion in a bidentate manner using the N2O2 chromophore. The effective magnetic moments (μeff) observed for the complexes are in the range of 4.20–5.30 BM. Electronic spectra results and magnetic susceptibility measurements are consistent with the adoption of a four‐coordinate geometry for the cobalt(II) chelates and a six‐coordinate octahedral geometry for the 2,2′‐bipyridine and 1,10‐phenanthroline adducts. The available conductance data in nitromethane indicates that the compounds are non‐electrolytes.
{"title":"Synthesis and Physicochemical Properties of Some β‐Ketoaminato Cobalt(II) Chelates and Their Adducts with 2,2′‐Bipyridine and 1,10‐Phenanthroline","authors":"J. Woods, A. Osowole, O. A. Odunola","doi":"10.1081/SIM-200026294","DOIUrl":"https://doi.org/10.1081/SIM-200026294","url":null,"abstract":"Abstract The cobalt(II) β‐ketoamines complexes {Co[CH3C(O)CHC(CH3)NR]2; R = CH3, CH2(OH)CH2, C4H9} and ketoiminates {Co[CH3C(O)CH(CH3)C(‐N(CH2) n N‐)C(CH3)CHC(O)CH3]} and their adducts with 2,2′‐bipyridine (bipy) and 1,10‐phenanthroline (phen) have been synthesized and characterized by elemental analyses, magnetic susceptibility, conductivity, infrared, and electronic spectral measurements. The ligands coordinate to the cobalt ion in a bidentate manner using the N2O2 chromophore. The effective magnetic moments (μeff) observed for the complexes are in the range of 4.20–5.30 BM. Electronic spectra results and magnetic susceptibility measurements are consistent with the adoption of a four‐coordinate geometry for the cobalt(II) chelates and a six‐coordinate octahedral geometry for the 2,2′‐bipyridine and 1,10‐phenanthroline adducts. The available conductance data in nitromethane indicates that the compounds are non‐electrolytes.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"12 1","pages":"1471 - 1485"},"PeriodicalIF":0.0,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76403763","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}
M. Mashaly, Atef T. Ramadan, B. A. El‐Shetary, Areej K. Dawoud
Abstract The reactions of azo ligand, 2‐[2′‐carboxyphenylazo]‐5,5‐dimethyl‐1,3‐cyclohexane‐dione, (H2L), with the metal ion Cd(II), Cu(II), Ni(II), Co(II), Th(IV), or UO2(VI) in the presence of LiOH as a deprotonating agent, yielded binary mononuclear complexes. The binary Cu(II) complex reacts with the ligands 1,10‐phenanthroline or 2‐aminopyridine to form mixed‐ligand complexes. All the binary complexes of Cd(II), Cu(II), and Ni(II) have octahedral configurations, while the Co(II) complex is square‐planar. The binary complexes of Th(IV) and UO2(VI) have distorted dodecahedral geometries. The mixed‐ligand complexes have octahedral configurations. Thermal studies on these complexes showed the possibility of obtaining new complexes pyrolytically, where the complexes decompose through several isolable as well as non‐isolable intermediates during heating. The structures of all complexes and the corresponding thermal products 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 ligand and some of the complexes were found to activate the enzyme pectinlyase.
{"title":"Azo Complexes of Cu(II), Co(II), Ni(II), Cd(II), Th(IV), and UO2(VI) Ions. Mixed‐Ligand Complexes, Pyrolysis Products and Biological Activity","authors":"M. Mashaly, Atef T. Ramadan, B. A. El‐Shetary, Areej K. Dawoud","doi":"10.1081/SIM-200026204","DOIUrl":"https://doi.org/10.1081/SIM-200026204","url":null,"abstract":"Abstract The reactions of azo ligand, 2‐[2′‐carboxyphenylazo]‐5,5‐dimethyl‐1,3‐cyclohexane‐dione, (H2L), with the metal ion Cd(II), Cu(II), Ni(II), Co(II), Th(IV), or UO2(VI) in the presence of LiOH as a deprotonating agent, yielded binary mononuclear complexes. The binary Cu(II) complex reacts with the ligands 1,10‐phenanthroline or 2‐aminopyridine to form mixed‐ligand complexes. All the binary complexes of Cd(II), Cu(II), and Ni(II) have octahedral configurations, while the Co(II) complex is square‐planar. The binary complexes of Th(IV) and UO2(VI) have distorted dodecahedral geometries. The mixed‐ligand complexes have octahedral configurations. Thermal studies on these complexes showed the possibility of obtaining new complexes pyrolytically, where the complexes decompose through several isolable as well as non‐isolable intermediates during heating. The structures of all complexes and the corresponding thermal products 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 ligand and some of the complexes were found to activate the enzyme pectinlyase.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"12 1","pages":"1349 - 1378"},"PeriodicalIF":0.0,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75233236","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 interaction of thorium(IV) salts with 4[N‐(benzylidene)amino]antipyrine semicarbazone (BAAPS), 4[N‐(4′‐methoxybenzylidene)amino]antipyrine semicarbazone (MBAAPS), 4[N‐(4′‐dimethoxyaminobenzylidene)amino]antipyrine semicarbazone (DABAAPS), 4[N‐(2′‐nitrobenzylidene)amino]antipyrine semicarbazone (2′‐NO2BAAPS), and 4[N‐(3′‐nitrobenzylidene)amino]antipyrine semicarbazone (3′‐NO2BAAPS) in non‐aqueous solvents resulted in the formation of [ThL2X4] (X = Cl, Br, or NCS), [ThL2I2]I2, [ThL2](ClO4)2 or [ThL(NO3)4] (L = BAAPS, MBAAPS, DABAAPS, 2‐NO2BAAPS, or 3‐NO2BAAPS). All of these compounds were characterized by elemental analyses, electrical conductivity, IR, and thermal methods. X‐ray powder diffraction studies of a representative complex were also undertaken. Th(IV) displays the coordination numbers 6, 8, 10, and 11 in these compounds depending on the nature of the coordinated anion and the stoichiometry.
{"title":"Studies on Some Thorium(IV) Complexes with High Coordination Numbers Derived from Semicarbazones of 4‐Aminoantipyrine","authors":"R. Agarwal, I. Chakraborti, H. Agarwal","doi":"10.1081/SIM-200026274","DOIUrl":"https://doi.org/10.1081/SIM-200026274","url":null,"abstract":"Abstract The interaction of thorium(IV) salts with 4[N‐(benzylidene)amino]antipyrine semicarbazone (BAAPS), 4[N‐(4′‐methoxybenzylidene)amino]antipyrine semicarbazone (MBAAPS), 4[N‐(4′‐dimethoxyaminobenzylidene)amino]antipyrine semicarbazone (DABAAPS), 4[N‐(2′‐nitrobenzylidene)amino]antipyrine semicarbazone (2′‐NO2BAAPS), and 4[N‐(3′‐nitrobenzylidene)amino]antipyrine semicarbazone (3′‐NO2BAAPS) in non‐aqueous solvents resulted in the formation of [ThL2X4] (X = Cl, Br, or NCS), [ThL2I2]I2, [ThL2](ClO4)2 or [ThL(NO3)4] (L = BAAPS, MBAAPS, DABAAPS, 2‐NO2BAAPS, or 3‐NO2BAAPS). All of these compounds were characterized by elemental analyses, electrical conductivity, IR, and thermal methods. X‐ray powder diffraction studies of a representative complex were also undertaken. Th(IV) displays the coordination numbers 6, 8, 10, and 11 in these compounds depending on the nature of the coordinated anion and the stoichiometry.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"77 1","pages":"1431 - 1452"},"PeriodicalIF":0.0,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"79238822","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 series of 18‐membered octaazamacrocyclic complexes [ML1X2] and [ML2X2] (M = Mn(II), Co(II), Ni(II), Cu(II), and Zn(II); X = Cl or NO3) have been synthesized by template condensation of o‐phthalaldehyde with hydrazine hydrate and formaldehyde or acetaldehyde in MeOH. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, FT‐IR, 1H NMR, EPR, UV spectroscopy, magnetic susceptibility, and conductivity measurements. An octahedral geometry has been suggested for all the complexes and the observed low molar conductance values indicate their non‐ionic nature.
{"title":"Synthesis and Physico‐Chemical Studies on 18‐Membered Octaazamacrocyclic Complexes of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) Ions","authors":"T. Khan, S. Tabassum, Y. Azim, M. Shakir","doi":"10.1081/SIM-200026200","DOIUrl":"https://doi.org/10.1081/SIM-200026200","url":null,"abstract":"Abstract A new series of 18‐membered octaazamacrocyclic complexes [ML1X2] and [ML2X2] (M = Mn(II), Co(II), Ni(II), Cu(II), and Zn(II); X = Cl or NO3) have been synthesized by template condensation of o‐phthalaldehyde with hydrazine hydrate and formaldehyde or acetaldehyde in MeOH. The nature of bonding and the stereochemistry of the complexes have been deduced from elemental analyses, FT‐IR, 1H NMR, EPR, UV spectroscopy, magnetic susceptibility, and conductivity measurements. An octahedral geometry has been suggested for all the complexes and the observed low molar conductance values indicate their non‐ionic nature.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"27 1","pages":"1305 - 1318"},"PeriodicalIF":0.0,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88898323","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 reactions of the lanthanide(III) ions Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, and Yb, with pyridine‐2‐carboxaldehyde‐4‐chlorobenzoylhydrazone (PpClBH) leads to the formation of complexes corresponding to the formulae [Ln(PpClBH)2(NO3)3], (Ln = La, Ce, and Pr) and [Ln(PpClBH)2(NO3)2]NO3 (Ln = Y, Nd, Eu, Gd, Tb, Dy, Ho, Er, and Yb). Twelve new compounds have been prepared. The complexes were characterized by means of elemental analyses, conductivity measurements, magnetic moments, and spectroscopic studies (IR, UV‐VIS, and 1H NMR). The coordination number of 12 have been proposed for the La, Ce, and Pr complexes, while for the Y, Nd, Eu, Gd, Tb, Dy, Ho, Er, and Yb compounds the coordination number is reduced to 10. This change in coordination number is consistent with the lanthanide contraction. Complexes having coordination numbers greater than ten appear to be limited to the lighter lanthanides. PpClBH has been characterized by elemental analysis, IR, UV, and 1H NMR.
{"title":"Synthetic and Spectroscopic Studies of Some Nitrato–Lanthanide(III) Hydrazone Complexes of Higher Coordination Number","authors":"D. Paschalidis","doi":"10.1081/SIM-200026268","DOIUrl":"https://doi.org/10.1081/SIM-200026268","url":null,"abstract":"Abstract The reactions of the lanthanide(III) ions Y, La, Ce, Pr, Nd, Eu, Gd, Tb, Dy, Ho, Er, and Yb, with pyridine‐2‐carboxaldehyde‐4‐chlorobenzoylhydrazone (PpClBH) leads to the formation of complexes corresponding to the formulae [Ln(PpClBH)2(NO3)3], (Ln = La, Ce, and Pr) and [Ln(PpClBH)2(NO3)2]NO3 (Ln = Y, Nd, Eu, Gd, Tb, Dy, Ho, Er, and Yb). Twelve new compounds have been prepared. The complexes were characterized by means of elemental analyses, conductivity measurements, magnetic moments, and spectroscopic studies (IR, UV‐VIS, and 1H NMR). The coordination number of 12 have been proposed for the La, Ce, and Pr complexes, while for the Y, Nd, Eu, Gd, Tb, Dy, Ho, Er, and Yb compounds the coordination number is reduced to 10. This change in coordination number is consistent with the lanthanide contraction. Complexes having coordination numbers greater than ten appear to be limited to the lighter lanthanides. PpClBH has been characterized by elemental analysis, IR, UV, and 1H NMR.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"16 1","pages":"1401 - 1415"},"PeriodicalIF":0.0,"publicationDate":"2004-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80794611","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 novel dioxime, 1,2‐dihydroxyimino‐3‐aza‐6‐morpholine heptane (H2L) was synthesized by the reaction of anti‐monochloroglyoxime and 4‐(3‐aminopropyl)morpholine in absolute THF. Mononuclear complexes with a metal:ligand ratio of 1:2 were prepared with Co(II), Cu(II), and Ni(II). The ligand and complexes were characterized by elemental analyses, FT‐IR, UV‐Vis, 1H NMR and 13C NMR spectra, magnetic susceptibility measurements. The thermal behavior of the compounds has been studied by thermogravimetry (TGA).
{"title":"Synthesis of a Novel Oxime Ligand: Characterization and Investigation of Its Complexes with Some Metal Ions","authors":"E. Taş, M. Ulusoy, M. Guler","doi":"10.1081/SIM-120039267","DOIUrl":"https://doi.org/10.1081/SIM-120039267","url":null,"abstract":"Abstract A novel dioxime, 1,2‐dihydroxyimino‐3‐aza‐6‐morpholine heptane (H2L) was synthesized by the reaction of anti‐monochloroglyoxime and 4‐(3‐aminopropyl)morpholine in absolute THF. Mononuclear complexes with a metal:ligand ratio of 1:2 were prepared with Co(II), Cu(II), and Ni(II). The ligand and complexes were characterized by elemental analyses, FT‐IR, UV‐Vis, 1H NMR and 13C NMR spectra, magnetic susceptibility measurements. The thermal behavior of the compounds has been studied by thermogravimetry (TGA).","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"10 1","pages":"1211 - 1221"},"PeriodicalIF":0.0,"publicationDate":"2004-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84521810","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 copper(II)–manganese(II) heterobinuclear complexes bridged by N,N′‐bis[2‐(dimethylamino)ethyl]oxamido dianion (dmoxae) and end‐capped with 5‐nitro‐1,10‐phenanthroline (NO2phen), 2,9‐dimethyl‐1,10‐phenanthroline (Me2phen) or 5‐phenyl‐1,10‐phenanthroline (Phphen), respectively; namely, [Cu(dmoxae)Mn(NO2phen)2](ClO4)2 (1), [Cu(dmoxae)Mn(Me2phen)2](ClO4)2 (2), and [Cu(dmoxae)Mn(Phphen)2](ClO4)2 (3); have been synthesized and characterized by elemental analyses, IR and electronic spectral studies and molar conductivity measurements. It is proposed that these complexes have oxamido‐bridged structures consisting of planar copper(II) and octahedral manganese(II) ions. The electronic reflectance spectra indicate the presence of exchange–coupling interaction between bridging copper(II) and manganese(II) ions. The cryomagnetic measurements (4.2–300 K) of the three complexes demonstrated the operation of antiferromagnetic interaction between the adjacent manganese(II) and copper(II) ions through the oxamido‐bridge within these copper(II)–manganese(II) heterobinuclear complexes. On the basis of the spin Hamiltonian, Hˆ= − 2Sˆ1 · Sˆ2, a magnetic analysis was carried out for the three complexes and the spin‐coupling constant (J) was evaluated as −39.7 cm−1 for (1), −38.5 cm−1 for (2), and −37.8 cm−1 for (3). The influence of methyl substituents in amine groups of the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.
摘要:三种新的铜(II) -锰(II)杂双核配合物分别以N,N′-二[2‐(二甲氨基)乙基]氧胺二碘离子(dmoxae)桥接，末端分别以5‐硝基‐1,10‐菲罗啉(NO2phen)、2,9‐二甲基‐1,10‐菲罗啉(Me2phen)或5‐苯基‐1,10‐菲罗啉(Phphen)为封端;即[Cu(dmoxae)Mn(NO2phen)2](ClO4)2 (1)， [Cu(dmoxae)Mn(Me2phen)2](ClO4)2 (2)， [Cu(dmoxae)Mn(Phphen)2](ClO4)2 (3);通过元素分析、红外光谱和电子光谱研究以及摩尔电导率测量对其进行了合成和表征。提出这些配合物具有由平面铜(II)和八面体锰(II)离子组成的氧胺桥接结构。电子反射光谱表明桥接铜(II)和锰(II)离子之间存在交换耦合相互作用。三种配合物的低温磁测量(4.2-300 K)证明了相邻的锰(II)和铜(II)离子之间通过铜(II) -锰(II)异双核配合物内的氧胺桥发生反铁磁相互作用。根据自旋哈密顿量H = - 2S - 1·S - 2，对这三种配合物进行了磁分析，得到自旋耦合常数J分别为- 39.7 cm - 1(1)、- 38.5 cm - 1(2)和- 37.8 cm - 1(3)。本文还讨论了桥接配体胺基甲基取代基对这类配合物金属离子间磁相互作用的影响。
{"title":"Synthesis and Magnetic Studies of μ‐Oxamido‐bridged Copper(II)–Manganese(II) Heterobinuclear Complexes","authors":"Yan-Tuan Li, Cui‐Wei Yan, Chunyuan Zhu, H. Guan","doi":"10.1081/SIM-120039264","DOIUrl":"https://doi.org/10.1081/SIM-120039264","url":null,"abstract":"Abstract Three new copper(II)–manganese(II) heterobinuclear complexes bridged by N,N′‐bis[2‐(dimethylamino)ethyl]oxamido dianion (dmoxae) and end‐capped with 5‐nitro‐1,10‐phenanthroline (NO2phen), 2,9‐dimethyl‐1,10‐phenanthroline (Me2phen) or 5‐phenyl‐1,10‐phenanthroline (Phphen), respectively; namely, [Cu(dmoxae)Mn(NO2phen)2](ClO4)2 (1), [Cu(dmoxae)Mn(Me2phen)2](ClO4)2 (2), and [Cu(dmoxae)Mn(Phphen)2](ClO4)2 (3); have been synthesized and characterized by elemental analyses, IR and electronic spectral studies and molar conductivity measurements. It is proposed that these complexes have oxamido‐bridged structures consisting of planar copper(II) and octahedral manganese(II) ions. The electronic reflectance spectra indicate the presence of exchange–coupling interaction between bridging copper(II) and manganese(II) ions. The cryomagnetic measurements (4.2–300 K) of the three complexes demonstrated the operation of antiferromagnetic interaction between the adjacent manganese(II) and copper(II) ions through the oxamido‐bridge within these copper(II)–manganese(II) heterobinuclear complexes. On the basis of the spin Hamiltonian, Hˆ= − 2Sˆ1 · Sˆ2, a magnetic analysis was carried out for the three complexes and the spin‐coupling constant (J) was evaluated as −39.7 cm−1 for (1), −38.5 cm−1 for (2), and −37.8 cm−1 for (3). The influence of methyl substituents in amine groups of the bridging ligand on magnetic interactions between the metal ions of this kind of complexes is also discussed.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"29 1","pages":"1165 - 1179"},"PeriodicalIF":0.0,"publicationDate":"2004-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90985177","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 Rates for the reactions of M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph, C5H5N or M = Mn, L = C5H5N) with L in the presence of (CH3)3NO as O‐atom transfer reagent and CHCl3 as solvent are reported. The reaction rates suggest a pathway of association (k 2). The reaction rate order of Re2(CO)9L with the four ligands is as follows: PPh3 > PMePh2 > PMe2Ph > C5H5N.
摘要报道了M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph, C5H5N或M = Mn, L = C5H5N)与L在(CH3)3NO为O原子转移试剂，CHCl3为溶剂下的反应速率。Re2(CO)9L与四种配体的反应速率顺序为:PPh3 > PMePh2 > PMe2Ph > C5H5N。
{"title":"Oxygen Atom Transfer Reactions to Metal Carbonyls: Kinetics and Mechanism of CO Substitution Reactions of M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph, C5H5N, or M = Mn, L = C5H5N) in the Presence of (CH3)3NO","authors":"Lijun Peng, Yici. Gao","doi":"10.1081/SIM-120039265","DOIUrl":"https://doi.org/10.1081/SIM-120039265","url":null,"abstract":"Abstract Rates for the reactions of M2(CO)9L (M = Re, L = PPh3, PMePh2, PMe2Ph, C5H5N or M = Mn, L = C5H5N) with L in the presence of (CH3)3NO as O‐atom transfer reagent and CHCl3 as solvent are reported. The reaction rates suggest a pathway of association (k 2). The reaction rate order of Re2(CO)9L with the four ligands is as follows: PPh3 > PMePh2 > PMe2Ph > C5H5N.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"34 1","pages":"1181 - 1190"},"PeriodicalIF":0.0,"publicationDate":"2004-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"88604700","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) complexes Mn[HB(pz)3]2 (1) (pz = pyrazole) and Mn[HB(3,5‐Me2‐pz)3]2 (2) have been obtained by the reaction of Mn(OOCCH3)2 with NaHB(pz)3 and NaHB(3,5‐Me2‐pz)3 in MeOH, respectively. The two complexes (1) and (2) were characterized by IR, elemental analyses, and x‐ray diffraction. Complex (1) crystallizes in the space group C2/c, a = 18.971(3) Å, b = 13.700(3) Å, c = 19.056(3) Å, β = 111.378(10), V = 4612.0(13) Å3, Z = 2. Complex (2) crystallizes in the space group R‐3, a = 10.9832(18) Å, b = 10.983(2) Å, c = 24.785(3) Å, γ = 120°, V = 2589.3(7) Å3, Z = 3. X‐ray structure analysis has shown that the complexes (1) and (2) all are monomeric neutral complexes, and possess similar coordination modes around the metal Mn centers. In addition, some related bonding distances, angles, and structural properties are discussed.
摘要Mn(OOCCH3)2分别与NaHB(pz)3和NaHB(3,5‐Me2‐pz)3在MeOH中反应得到Mn(II)配合物Mn[HB(pz)3]2 (1) (pz =吡唑)和Mn[HB(3,5‐Me2‐pz)3]2(2)。两个配合物(1)和(2)通过红外光谱、元素分析和x射线衍射进行了表征。配合物(1)在C2/c空间群中结晶，a = 18.971(3) Å， b = 13.700(3) Å， c = 19.056(3) Å， β = 111.378(10)， V = 4612.0(13) Å3, Z = 2。配合物(2)在空间群R‐3中结晶，a = 10.9832(18) Å， b = 10.983(2) Å， c = 24.785(3) Å， γ = 120°，V = 2589.3(7) Å3, Z = 3。X射线结构分析表明，配合物(1)和(2)均为单体中性配合物，在金属Mn中心周围具有相似的配位模式。此外，还讨论了相关的键距、键角和结构性能。
{"title":"Synthesis and Structure of the Mn(II) Complexes with Tripyrazolylborate Ligands: Mn[HB(pz)3]2 and Mn[HB(3,5‐Me2‐pz)3]2","authors":"Y. Xing, K. Aoki, F. Bai","doi":"10.1081/SIM-120039263","DOIUrl":"https://doi.org/10.1081/SIM-120039263","url":null,"abstract":"Abstract Mn(II) complexes Mn[HB(pz)3]2 (1) (pz = pyrazole) and Mn[HB(3,5‐Me2‐pz)3]2 (2) have been obtained by the reaction of Mn(OOCCH3)2 with NaHB(pz)3 and NaHB(3,5‐Me2‐pz)3 in MeOH, respectively. The two complexes (1) and (2) were characterized by IR, elemental analyses, and x‐ray diffraction. Complex (1) crystallizes in the space group C2/c, a = 18.971(3) Å, b = 13.700(3) Å, c = 19.056(3) Å, β = 111.378(10), V = 4612.0(13) Å3, Z = 2. Complex (2) crystallizes in the space group R‐3, a = 10.9832(18) Å, b = 10.983(2) Å, c = 24.785(3) Å, γ = 120°, V = 2589.3(7) Å3, Z = 3. X‐ray structure analysis has shown that the complexes (1) and (2) all are monomeric neutral complexes, and possess similar coordination modes around the metal Mn centers. In addition, some related bonding distances, angles, and structural properties are discussed.","PeriodicalId":22160,"journal":{"name":"Synthesis and Reactivity in Inorganic and Metal-organic Chemistry","volume":"150 1","pages":"1149 - 1163"},"PeriodicalIF":0.0,"publicationDate":"2004-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"86498357","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：