The title complex [Mn(phen)2(H2O)2](OAc)26H2O (phen = 1,10-phenanthroline, C12H8N2, OAc = acetate, C2H3O2) with formula C28H38MnN4O12 and Mr = 677.56 has been syn- thesized and structurally characterized by X-ray diff...The title complex [Mn(phen)2(H2O)2](OAc)26H2O (phen = 1,10-phenanthroline, C12H8N2, OAc = acetate, C2H3O2) with formula C28H38MnN4O12 and Mr = 677.56 has been syn- thesized and structurally characterized by X-ray diffraction. The crystal is of triclinic, space group P ?with a = 9.6201(5), b = 13.4663(7), c = 14.5375(8) , a = 108.428(1), b =93.898(1), g = 110.492(1), V = 1639.5(2) ?, Dc = 1.373 g/cm3, F(000) = 710, = 0.468 cm-1 and Z = 2. The final refinement gave R = 0.0522 and wR = 0.1259 for 4714 observed reflections with I > 2s(I). It consists of discrete [Mn(phen)2(H2O)2]2+ cation, two acetate anions and six lattice water molecules. The MnII ion coordinated by four nitrogen atoms from two chelating phen and two oxygen atoms from two cis-related water molecules is in a distorted octahedral coordination environment. Two OAc- anions and six water molecules exist outside the [Mn(phen)2(H2O)2]2+ cation as counter ions and solvate molecules, respectively. The cations and anions are interconnected by the solvate water molecules which are hydrogen bonded to both aqua ligands and acetate oxygen atoms, building up the crystals of this compound to be a supramolecule-like aggregate.展开更多
A dinuclear manganese（Ⅱ） complex, [Mn2（μ-OAc）2（phen）4]（ClO4）2 1 （phen = phenanthroline）, has been prepared by the reaction of Mn（OAc）2-4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. ...A dinuclear manganese（Ⅱ） complex, [Mn2（μ-OAc）2（phen）4]（ClO4）2 1 （phen = phenanthroline）, has been prepared by the reaction of Mn（OAc）2-4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. The crystal structure has been determined by X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 9.6052（4）, b = 14.2353（7）, c = 18.8893（8） A, β= 96.584（1）° C52H38C12Mn2N8O12, Mr = 1147.68, V= 2565.8（2） A^3, Dc = 1.486 g/cm^3, F（000） = 1172,μ = 0.668 cm^-1 and Z = 2. The final refinement gave R = 0.0605 and wR = 0.1619 for 3203 reflections with I 〉 2σ（I）. The complex contains a dinuclear [Mn2（μ-OAc）2（phen）4]]^2＋ cation located at a centre of symmetry with two syn-anti acetate bridges between the Mn atoms. Each Mn atom is coordinated by four N atoms from two chelating phen ligands and two O atoms from a pair of bridging acetate groups to furnish a distorted octahedral geometry. Two ClO4 anions exist around the cation [Mn2（μ-OAc）2（phen）4]^2＋ as counter ions.展开更多
The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of ...The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of the complex in N, N-dimethylformamide solution was investigated. The results show that lower temperature is in favor of the oxygenation, and energy, enthalpy and entropy are -3.8 kJ/mol, -4.2 J/mol and -161.44 J/(mol·K), respectively. In the presence of the manganese complex, dehydroepiandrosterone acetate is effectively oxidized by molecular oxygen and the corresponding enone 7-ketodehydroepiandrosterone acetate is obtained. The yield is 62.1% when the oxidation is carried out under the reaction conditions of 60 ℃, 2 MPa of O2 pressure, C5H5N as a solvent and molar ratio of the substrate to the complex of 1:10.展开更多
基金This work was supported by the State Key Basic Research and Development Plan (G1998010100) and NNSFC+5 种基金 (No. 30170229) and Expert Project of Key Basic Research from Ministry of Sci.& Tech.
文摘The title complex [Mn(phen)2(H2O)2](OAc)26H2O (phen = 1,10-phenanthroline, C12H8N2, OAc = acetate, C2H3O2) with formula C28H38MnN4O12 and Mr = 677.56 has been syn- thesized and structurally characterized by X-ray diffraction. The crystal is of triclinic, space group P ?with a = 9.6201(5), b = 13.4663(7), c = 14.5375(8) , a = 108.428(1), b =93.898(1), g = 110.492(1), V = 1639.5(2) ?, Dc = 1.373 g/cm3, F(000) = 710, = 0.468 cm-1 and Z = 2. The final refinement gave R = 0.0522 and wR = 0.1259 for 4714 observed reflections with I > 2s(I). It consists of discrete [Mn(phen)2(H2O)2]2+ cation, two acetate anions and six lattice water molecules. The MnII ion coordinated by four nitrogen atoms from two chelating phen and two oxygen atoms from two cis-related water molecules is in a distorted octahedral coordination environment. Two OAc- anions and six water molecules exist outside the [Mn(phen)2(H2O)2]2+ cation as counter ions and solvate molecules, respectively. The cations and anions are interconnected by the solvate water molecules which are hydrogen bonded to both aqua ligands and acetate oxygen atoms, building up the crystals of this compound to be a supramolecule-like aggregate.
文摘A dinuclear manganese（Ⅱ） complex, [Mn2（μ-OAc）2（phen）4]（ClO4）2 1 （phen = phenanthroline）, has been prepared by the reaction of Mn（OAc）2-4H2O, phen, tartaric acid and NaClO4·H2O in MeOH/H2O solution. The crystal structure has been determined by X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 9.6052（4）, b = 14.2353（7）, c = 18.8893（8） A, β= 96.584（1）° C52H38C12Mn2N8O12, Mr = 1147.68, V= 2565.8（2） A^3, Dc = 1.486 g/cm^3, F（000） = 1172,μ = 0.668 cm^-1 and Z = 2. The final refinement gave R = 0.0605 and wR = 0.1619 for 3203 reflections with I 〉 2σ（I）. The complex contains a dinuclear [Mn2（μ-OAc）2（phen）4]]^2＋ cation located at a centre of symmetry with two syn-anti acetate bridges between the Mn atoms. Each Mn atom is coordinated by four N atoms from two chelating phen ligands and two O atoms from a pair of bridging acetate groups to furnish a distorted octahedral geometry. Two ClO4 anions exist around the cation [Mn2（μ-OAc）2（phen）4]^2＋ as counter ions.
基金Project(76132020) supported by the Post-Doctoral Science Fund of Central South University
文摘The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of the complex in N, N-dimethylformamide solution was investigated. The results show that lower temperature is in favor of the oxygenation, and energy, enthalpy and entropy are -3.8 kJ/mol, -4.2 J/mol and -161.44 J/(mol·K), respectively. In the presence of the manganese complex, dehydroepiandrosterone acetate is effectively oxidized by molecular oxygen and the corresponding enone 7-ketodehydroepiandrosterone acetate is obtained. The yield is 62.1% when the oxidation is carried out under the reaction conditions of 60 ℃, 2 MPa of O2 pressure, C5H5N as a solvent and molar ratio of the substrate to the complex of 1:10.
