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1.
Six new μ-phthalato binuclear oxovanadium(IV) complexes, namely [(VO)2(PHTH)-(L)2]SO4 (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2 bpy); 5-nitro-1,10-phenanthroline (NO2-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-methyl-1,10-phenanthroline (CH3-phen), where PHTH is the phthalate dianion), have been synthesized and characterized by elemental analyses, IR, electronic spectra, magnetic moments at room temperature and molar conductivity measurements. The temperature dependence of the magnetic susceptibility of complexes [(VO)2(PHTH)(phen)2]SO4 (1) and [(VO)2(PHTH)(CH3-phen)2]SO4 (2) was measured in 4—300 K range and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, ?=?2J?1·?2, giving the exchange integrals J=?12.8 cm?1 for 1 and J=?7.9 cm?l for 2. This indicates an antiferromagnetic spin-exchange interaction between the metal ions within each molecule.  相似文献   

2.
Six novel oxovanadium(IV) binuclear complexes have been synthesized and characterized,namely,[(VO)2(CA)La]SO4 [L denotes 5-methyl-l,10-phenanthroline (Me-phen);2,9-dimethyl-1,10-phenanthroline (Me2-phen); 5-chloro-l,10-phenanthroline (Cl-phen); diaminoethane (en); 1,3-diaminopropane (pn) and 1,2-diaminopropane (ap) respectively.],where CA represents the dianion of chloranilic acid.Based on elemental analyses,molar conductivity and room temperature magnetic moment measurements,IR and electronic spectral studies,it is proposed that these complexes have CA-bridged structures and consist of two vanadium(IV) ions in a square-pyramidal environment.The complexes [(VO)2(CA)(Me-phen)2]SO4 (1) and [(VO)2(CA)(Me2-phen)2]SO4 (2) were characterized by variable temperature magnetic susceptibility measurements (4~300 K) and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares method,giving the exchange integral J=-15.8 cm-1 for 1 and J=-10.6 cm-1 for 2.This result indicates that t  相似文献   

3.
Five oxovanadium(IV) dinuclear complexes described by the overall formula [(VO)2(IA)L2SO4, where IA repents the dianion of iodanilic acid and L denotes 2, 2′-bipyridine (bpy); 4,4′-dimethy12,2′-bipyridine (Meo-bpy); 1,10-phenanthroline (phen); 4,7-diphenyl-l, 10-phenanthroline (Ph2-phen) and 5-nitro-1, 10-phenanthroline (NO2-phen), have been synthesized and characterized by elemental analyses, molar conductivity and roomtemperature magnetic moment measurements, IR and electronic spectral studies. It is proposed that these complexes have IA-bridged structures and consist of two oxovanadium(IV) ions each in a square pyramidal environment. The complexes (VO)2(IA) (bpy)2]SO4, (1) and[(VO)2( IA) (phen)2 ]SO4 (2) were further characterized by variable temperature (4.2–300 K) magnetic susceptibility measurements and the observed data were fitted to the modified Bleaney-Bowers equation by the least-squares method, giving the exchange integral J = - 2.15 m?1 for 1 and J = - 9.88 cm?1 for 2. This result indicates that there is a weak antiferromagnetic spin-exchange interaction between the two VO2+ ions within each molecule.  相似文献   

4.
Five chloroanilato-bridged manganese(II) binuclear complexes, [Mn2(CA)L4](ClO4)2, where L = 4,4′-dimethyl-2,2′-bipyridine (Me2-bpy), 5-methyl-1,10-phenanthroline (Me-phen), 5-chloro-1,10-phenanthroline (Cl-phen), 5-nitro-1,10-phenanthroline (NO2-phen) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen), and CA represents the dianion of chloroanilic acid, have been synthesized and characterized by elemental analyses, molar conductivity and room temperature magnetic moment measurements, and by spectroscopy. It is proposed that these complexes have CA-bridged structures and consist of two manganese(II) ions in a distorted-octahedral environment. The complexes [Mn2(CA)(Me2-bpy)4](ClO4)2 (1) and [Mn2(CA)(Me-phen)4](ClO4)2 (2) were characterized by variable temperature magnetic susceptibility measurements (4–300 K) and the observed data were successfully simulated by an equation based on the spin Hamiltonian operator, Ĥ = −2 1 Ŝ 2, giving the exchange integral J = −1.98 cm−1 for (1) and J = −2.41 cm−1 for (2). This result indicates that there is a weak antiferromagnetic spin-exchange interaction between the two MnII ions within each molecule. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

5.
Four novel oxovanadium(IV) binuclear complexes have been synthesized, namely [(VO)2(IPHTA) (L)2SO4 (L denotes 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2bpy) and 5-nitro-1,10-phenanthroline (NO2-phen)), where IPHTA is the isophthalate dianon. Based on elemental analyses, molar conductivity measurements, IR and electronic spectra studies, it is proposed that these complexes have IPHTA-bridged structures and consist of two vanadium(IV) atoms in a square-pyramidal environment. The complexes [(VO)2(IPHTA)(Me2bpy)2]SO4 (1) and [(VO)2(IPHTA)(bpy)2]SO4 (2) were characterized by variable temperature magnetic susceptibility (4–300 K) and the data could be well fitted by the least-squares method to a susceptibility equation derived from the spin Hamiltonian operator, . The exchange integral, J, was found to be −26.8 cm−1 for (1) and −31.0 cm−1 for (2). These results are commensurate with antifferomagnetic interactions between two oxovanadium(IV) ions within each molecule. The influence of different terminal ligands on magnetic interactions between the metals of this kind of complexes is also discussed.  相似文献   

6.
Six new μ-terephthalato iron(III) binuclear complexes have been prepared and identified: [Fe2(TPHA)(L)4]-(ClO4)4 [L = 2,2′-bipyridine (bpy); 1,10-phenanthroline (phen); 4,4′-dimethyl-2,2′-bipyridine (Me2bpy); 5-methyl-1,10-phenanthroline (Me-phen); 5-chloro-1,10-phenanthroline (Cl-phen) and 5-nitro-1,10-phenanthroline (NO2-phen)]; where TPHA = the terephthalate dianion. Based on the elemental analyses, molar conductance and magnetic moments of room-temperature measurements, and spectroscopic studies, extended TPHA-bridged structures consisting of two iron(III) ions, each in an octahedral environment, are proposed for these complexes. The [Fe2(TPHA)(Me-phen)4](ClO4)4 (1) and [Fe2(TPHA)(phen)4](ClO4)4 (2) complexes were characterized by variable temperature magnetic susceptibility (4–300 K) measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, Ĥ = −2 1 Ŝ 2, giving the exchange integrals J = −1.05 cm−1 for (1) and J = −9.28 cm−1 for (2). This result indicates the presence of a weak antiferromagnetic spin-exchange interaction between the metal ions within each molecule. The influence of the terminal ligand methyl substituents on magnetic interactions between the metals is also discussed. This revised version was published online in June 2006 with corrections to the Cover Date.  相似文献   

7.
Four μ-2-chloroterephthalato binuclear iron(Ⅱ) complexes, namely [Fe2 (CTPHA) L4]-(ClO4)2, where L stands for 4,4'-dimethyl-2,2'-bipyridine (Me2-bpy); 2,9-dimethyl-l, 10-phenanthro-line (Me2-phen); 5-chloro-l, 10-phenanthroline (Cl-phen); 4, 7-diphenyl-l, 10-phenanthroline (Ph2-phen), respectively, and CTPHA represents 2-chlorolerephthalate dianion, have been synthesized and characterized. Based on the elemental analyses, molar conductance measurements and spectroscopic studies, extended CTPHA-bridged structures consisting of two iron(Ⅱ) ions, each in a distorted octahedral environment, are proposed for these complexes. [Fe2 CTPHA)-(Me2-bpy)4] (ClO2 (1) and [Fe2(CT-PHA)·(Me2-phen)4](ClO4)2 (2) complexes were characterized by variable temperature magnetic susceptibility (4-300 K) measurements and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = - 2JS1 · S2 , giving the exchange integrals J = - 1.28 cm-1 for 1 and J = - 1.85 cm-1 for 2. These r  相似文献   

8.
Four new u-oxamido heterobinuclear complexes have been synthesized and identified as [Cu(oxap)Fe(L)2]SO4, where oxap denotes the N, N'-bis(2-aminopropyl)oxamido dianion and L represents diaminoethane (en); 1,3-diaminopropane (pn); 1,2-diaminopropane (ap) and 2,9-dimethyl-1,10-phenanthroline (Me2-phen). Based on the elemental analyses, spectroscopic studies, magnetic moments (at room temperature) and molar conductivity measurements, extended oxamido-bridged structures consisting of a copper(Ⅱ) and an iron(Ⅱ) ions, which have a square planar environment and an octahedral environment, respectively, are proposed for these complexes. Complexes [Cu(oxap)Fe(en)2]SO4 (1) and [Cu(oxap)Fe(pn)2]SO4 (2) have been characterized by variable temperature magnetic susceptibility (4.2~300 K) and the observed data were least-squares fitted to the susceptibility equation derived from the spin Hamiltonian including single-ion zero-field interaction for the iron(Ⅱ) ion, H=-2JS1.S2-DSzl2, giving the exchange integrals J=-2  相似文献   

9.
Five new chloranilato-bridged binuclear chromium (III) complexes have been synthesized and identified as [Cr2(CA)L4]-(ClO4)4[L denotes 5-methyl-1,10-phenanthroline (Me-phen); 2,9-dimethyl-1, 10-phenanthroline ( Me2-phen); 5-chloro-1,10-phenanthroline(Cl-phen); diaminoethane (en) or 1,3-diaminopropane (pn)], where CA represents the dianion of chloranilic acid. Based on elemental analyses, molar conductivity and magnetic moment of room-temperature measurements, and IR and electronic spectral studies, it is proposed that these complexes have CA-bridged structures and consist of two chromium (III) ions, each in an octahedral environment. The complexes [Cr2(CA)(Me-phen)4](ClO4)4(1) and [Cr2(CA)(Me2-phen)4](ClO4)4(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, , giving the exchange parameter J = -7.8 cm-1 for (1) and J= -6.5 cm*1 for (2). This result  相似文献   

10.
Kong  Xiang-He  Yan  Cui-Wei  Li  Yan-Tuan  Liao  Dai-Zheng 《中国化学》1999,17(6):609-617
Seven new μ-isophthalato dinuclear lanthanide(III) complexes, namely [Ln2(IPHTA)(Me2-phen)4-(ClO4)2](ClO4)2 (Ln=La, Nd, Sm, Eu, Gd, Ho, Er), where Me2-phen denotes 2,9-dimethyl-1,10-phenanthroline (Me2-phen), IPHTA represents isophthalate dianion, have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, ESR and electronic spectra. The variable-temperature magnetic susceptibilities of [ Gd2 (IPHTA) (Me2-phen)4 ( ClO4 )2 ] ((ClO4 )2 complex were measured in the temperature range of 4–300 K and the observed data were successfully simulated by the equation based on the spin Hamiltonian operator, H = -2JS1. J2. giving the exchange parameter J = -0.19 cm?1. This result is commensurate with a weak antiferromagnetic spin-exchange interaction between Gd(III)-Gd(III) im within the complex.  相似文献   

11.
Four μ- oxamido heterodinuclear complexes, [Cu (oxae) Cr (L)2 ] (NO3) 3, where oxae denotes the N, N'bis (2-aminoethyl) oxamido dianion and L represents 1,10-phenanthroline (phen); 5-nitro-1,10-phenanthroline (NO2-phen); 5-methyl-1, 10-phenanthroline (Me-phen) and 2, 2′-bipyridine (bpy), have been synthesized and characterized by elemental analyses, magnetic moments (at room temperature) and molar conductivity measurements and spectroscopy. It is proposed that these complexes have extended oxamido-bridged structures consisting of a copper (II) ion and a chromium (III) ion, which have a square planar environment and octahedral environment, respectively. The cryomagnetic properties of the [Cu(oxae)Cr(bpy)2(NO3)3(1) and [Cu(oxae)Cr(phen)2](NO3)3(2) complexes have been measured over the range of 4.2–300 K. The leastsquares fit of the experimental data based on the spin Hamiltonian, ? = - 2J?1·?2, the exchange integrals (J) were evaluated as +36.9 cm?1 for 1 and +35.8 cm?1 for 2. The reds have connived that the spin coupling between the adjacent copper (II) and chromium (III) ions through oxamido-bridge in both 1 and 2 is ferromagnetic.  相似文献   

12.
The current article describes the synthesis and characterization of the following adducts: [Cd(2-mpipdtc)2(1,10-phen)], [Cd(2-mpipdtc)2(bipy)], [Cd(4-mpipdtc)2(1,10-phen)], [Cd(4-mpipdtc)2(bipy)] (where 2-mpipdtc? = 2-methylpiperidinecarbodithioate anion, 4-mpipdtc? = 4-methylpiperidinecarbodithioate anion, 1,10-phen = 1,10-phenanthroline and bipy = 2,2′-bipyridine). A single crystal X-ray structural analysis was carried out for [Cd(4-mpipdtc)2(1,10-phen)]. IR spectra of the complexes show the contribution of the thioureide form to the structures. Reduction in νC–N(thioureide) for the mixed ligand complexes is attributed to the change in coordination number from four to six and the steric effect exerted by 1,10-phenanthroline or 2,2′-bipyridine. Deshielding of the protons adjacent to nitrogen in the 1H NMR spectra is attributed to drift of electrons from the nitrogen of NR2, forcing electron density towards sulfur via the thioureide π-system. Single crystal X-ray structural analysis of [Cd(4-mpipdtc)2(1,10-phen)] showed that the cadmium is in a distorted octahedral environment with a CdS4N2 chromophore. The presence of 1,10-phenanthroline in the coordination sphere of Cd(dtc)2 increases the Cd–S distances and decreases the S–Cd–S angles. VBS analysis supports the determined structure.  相似文献   

13.
Summary Four new trinuclear copper(II) complexes bridged by o-phenylenebis(oxamato) (opba) and end-capped with 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen), 2,2-bipyridyl (bipy) or 4,4-dimethyl-2,2-bipyridyl (Me2bipy), {[Cu(opba)][Cu(L)]2}(ClO4)2 (L = phen, NO2-phen, bipy or Me2bipy), have been synthesized and characterized. Based on i.r., elemental analyses, conductivity measurements and electronic spectra, oxamato-bridged structures consisting of three copper(II) ions in which each copper(II) ion has a square-planar environment are proposed. The temperature-dependent magnetic susceptibility of {[Cu(opba)][Cu(phen)]2} (ClO4)2 has been studied in the 4.2–300 K range, giving the exchange integral J = -134.4cm–1. The result revealed the operation of an antiferromagnetic spin-exchange interaction between the adjacent copper ions.  相似文献   

14.
Vanadium complexes (VO)2(2,2′-bipy)2(bta)(H2O)2 (1) and (VO)2(1,10-phen)2(bta)(H2O)2 (2) (H4bta?=?1,2,4,5-benzenetetracarboxylic acid, 2,2′-bipy?=?2,2-bipyridine and 1,10-phen?=?1,10-phenanthroline) have been synthesized by the reaction of V2(SO4)3, H4bta, 2,2′-bipy (for 1) and 1,10-phen (for 2) by hydrothermal methods. The complexes were characterized by elemental analysis, IR, UV–vis, thermogravimetric analyses, and single-crystal X-ray diffraction. Structural analyses indicate that 1 and 2 are both VO-bta-N-heterocycle system complexes. The central vanadium is coordinated by N2O4 donors to form a distorted octahedral geometry. The complexes exhibit catalytic bromination activity in a single-pot reaction with conversion of phenol red to bromophenol blue in a mixed solution of H2O-DMF at 30?±?0.5?°C with pH 5.8, indicating that they can be considered as a functional model of vanadium-dependent haloperoxidases. The practical application of H2O2 detection has also been studied.  相似文献   

15.
Three new -oxalato-bridged heterotrinuclear copper(II)–iron(III)–copper(II) complexes have been synthesized and identified: [Cu2Fe(ox)3L2]ClO4 [L = 5-nitro-1,10-phenanthroline (NO2phen); 2,9-dimethyl-1,10-phenanthroline (Me2phen) or 2,2-bipyridine (bpy), respectively]; ox = the oxalato dianions. Based on elemental analyses, molar conductivity and magnetic moment (at room-temperature) measurements, i.r. and electronic spectral studies, extended ox-bridged structures consisting of two copper(II) and an iron(III) ions, in which the central iron(III) ion has an octahedral environment and the end-capped two copper(II) ions a square-planar environment, are proposed for these complexes. The [Cu2Fe(ox)3(Me2phen)2]ClO4 (1) and [Cu2Fe(ox)3(bpy)2]ClO4 (2) complexes were characterized further by variable-temperature magnetic susceptibility (4.2–300 K) measurements and the observed data were simulated by the equation based on the spin Hamiltonian operator, = –2J1 · 2, giving the exchange integrals J = –12.85 cm–1 for (1) and J = –11.28 cm–1 for (2). The results indicate the presence of an antiferromagnetic spin-exchange interaction between the copper(II) and iron(III) ions through the oxalato-bridge in both complexes (1) and (2).  相似文献   

16.
Summary The seven-coordinate complexes [MI2(CO)3(NCMe)2] (M=Mo or W) react with two equivalents of L(L=py, 4Me-py, 3Cl-py or 3Br-py) or one equivalent of NN {NN=2,2-bipyridine(bipy), 1,10-phenanthroline(phen), 5,6-dimethyl-1, 10-phenanthroline (5,6-Me2-1, 10-phen), 5-Nitro-1, 10-phenanthroline (5-NO2-1, 10-phen) and C6H4(o-NH2)2 (o-diam) (for M=Mo only)} in CH2Cl2 at room temperature to give the substituted products [MI2(CO)3L2] or [MI2(CO)3(NN)] (1–17) in high yield. The compounds [MI2(CO)3(NCMe)2] react with two equivalents of NN (for M=W, NN=bipy; for M=Mo, NN=phen) to give the dicationic salts [M(CO)3(NN)2]2I(18–19). The compounds [MI2(CO)3(NCMe)2] (M=Mo or W) react with two equivalents of 5,6-Me2-1, 10-phen to yield the monocationic dicarbonyl compounds [MI(CO)2(5,6-Me2-phen)2]I (20 and21). The dicationic mixed ligand complexes [M(CO)3(bipy)(5,6-Me2-phen)]2I (22 and23) are prepared by reacting [MI2(CO)3(NCMe)2] with one equivalent of bipy, followed by anin situ reaction with 5,6-Me2-1, 10-phen to afford the products22 and23. The complexes (1–23) described in this paper have been characterised by elemental analysis (C, H and N), i.r. spectroscopy and, in selected cases,1Hn.m.r. spectroscopy. Magnetic susceptibility measurements show the compounds to be diamagnetic.  相似文献   

17.
Quantum-chemical calculations of the 1,10-phenanthroline complexes [M(en)(1,10-phen)]2+ (M = Pt, Pd, Ni; en = NH2C2H4NH2) were performed by the DFT B3LYP method in the 6-31G** basis set using the GAMESS-2006 program package. The calculations were also performed for the nickel complexes with 2,2′-bi-1,10-phenanthroline, [Ni(2,2′-bi-1,10-phen)]2+, and with its electron-excessive analog, [Ni(2,2′-bi-1,10-phen)]0, and also for the octahedral complex cation [Ni(2,2′-bi-1,10-phen)Cl(H2O)]+ characterized by single crystal X-ray diffraction. For the Ni(II) complexes, the stabilities of their high-and low-spin isomers were evaluated, and the structural features were revealed. The barriers to mutual transformations of the low-and high-spin Ni(II) complexes are low.  相似文献   

18.
Shinsaku Yamazaki 《Polyhedron》1985,4(11):1915-1923
A series of potentially five-coordinate Pd(II) complexes, [Pd(PMe2Ph)3(2,9-R2-phen)][BF4]2 (R = H or Me; phen = 1,10-phenanthroline  相似文献   

19.
Four new heterotrinuclear complexes have been synthesized and characterized, namely {[Ni(L)2]2[Cu(opba)]}(ClO4)2, where opba denotes o-phenylenebis(oxamato) and L stands for 1,10-phenanthroline(phen) (1), 5-nitro-l,10-phenanthroline(NO2-phen) (2), 2,2′-bipyridyl(bpy) (S) and 4,4′-dimethyl-2,2′-bipyridyl(Me2bpy) (4). The temperature dependence of the magnetic susceptibility of {[Ni(phen)2]2[Cu(opba)]}(ClO4)23H2O has been studied in the 4–300 K range, giving the exchange integral J—109 cm?1. The HMT vs. T plot exhibits a minimum at about 100 K, characteristic of this kind of coupled polymetallic complex with an irregular spin-state structure.  相似文献   

20.
Summary Four novel trinuclear copper(II) complexes have been synthesized, namely {[Cu(pbaOH)][Cu(L)]2}(ClO4)2, where pbaOH = 2-hydroxy-1,3-propanediylbis(oxamato) and L is 1,10-phenanthroline (phen), 5-nitro-1,10-phenanthroline (NO2-phen), 2,2-bipyridyl (bipy) or 4,4-dimethyl-2,2-bipyridyl (Me2bipy). Based on i.r. and electronic spectra, elemental analyses, and conductivity measurements oxamato-bridged structures consisting of three copper(II) ions, in which each copper(II) ion has a square-planar environment, are proposed. The temperature-dependent magnetic susceptibility of {[Cu-(pbaOH)][Cu(phen)]2}(ClO4) 2 has been studied in the 4.2–300 K range, giving the exchange integral J=- 111.9cm–1. The result revealed the operation of an antiferromagnetic spin-exchange interaction between adjacent copper ions.  相似文献   

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