The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 ...The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 (2), c=18. 3773001 reflections The two [MnL(EtOH)]+ units are joined by one 4, 4'-bipyridine molecule to form a centrosymmetric binuclear complex cation [Mn2L2(EtOH)2 (bipy]2+. The coordination geometry around Mn atoms is a distorted octahe-dron with equatorial plane N2O2 from the Schiff base ligand L.展开更多
A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-cry...A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992（5）,b = 13.274（6）,c = 14.644（6） ,β = 115.198（4）o,V = 2285.2（16）3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F（000） = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections（Ⅰ 〉 2σ（Ⅰ））.X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn（3-meosalpn）（H2O）]＋ cations are linked by the central [Fe（CN）5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn（3-meo-salpn）（H2O）]＋ cations and [Fe（CN）5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.展开更多
A new complex [Mn（L）（NCS）]2·0.5CH3CN （H2L = N,N＇-bis（chlorosalicylidene）-1,2-diaminoethane） has been synthesized,and its structure （C70H51Cl8Mn4N13O8S4,Mr = 1833.84） was determined by single-crystal X-...A new complex [Mn（L）（NCS）]2·0.5CH3CN （H2L = N,N＇-bis（chlorosalicylidene）-1,2-diaminoethane） has been synthesized,and its structure （C70H51Cl8Mn4N13O8S4,Mr = 1833.84） was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system,space group C2/c with a = 25.883（2）,b = 12.3320（13）,c = 13.5951（16） ,β = 112.906（2）,V = 3997.2（7） 3,Z = 2,Dc = 1.524 g/cm3,μ（MoKα） = 1.050mm-1,F（000） = 1852,S = 1.098,the final R = 0.0630 and wR = 0.1847 for 2542 reflections with Ⅰ 〉 2σ（Ⅰ）. The centrosymmetric title complex contains a dimer in which two distorted octahedral Mn（Ⅲ） centers are bridged equatorially by phenolic oxygen of the Schiff base ligand. The units of the complex are linked via weak C-H···N hydrogen bonds,leading to the formation of 1D chains along the b axis. The weak π-π packing interactions and weak intermolecular C（3）-H（3）···N（3） hydrogen bonds stabilize the crystal structure.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
The title complex C_(27)H_(26)MnN_5O_2S (M_r= 539. 53 ) crystallizes in monoclinic system, space group P2_1/α with α = 8. 357 (2) A, b = 19. 077 (4) A . c = 16. 267(3) A, β=95. 85(2)°, V=2580(2) A￣3, Z=4, F(0...The title complex C_(27)H_(26)MnN_5O_2S (M_r= 539. 53 ) crystallizes in monoclinic system, space group P2_1/α with α = 8. 357 (2) A, b = 19. 077 (4) A . c = 16. 267(3) A, β=95. 85(2)°, V=2580(2) A￣3, Z=4, F(000) = 1120, D_c= 1. 39 g/ cm￣3 and μ=0. 601 mm￣(-1)(MoKα). The final R and R_w are 0. 0638 and 0. 0876, respectively. The coordination geometry around Mn atom is a distorted octahedron with a equatorial plane N_2O_2 from the Schiff base ligand bzacen￣(2-), the axial atoms being two nitrogen atoms from a thiocyanate and a pyrimidine ligand. The shifts of v_c=N, v_c=O and v_c=C to lower frequencies in IR and Raman spectra indicate that the ligand bzacen￣(2-) has been coordinated to Mn atom through its nitrogen and oxygen atoms. The lines assigned to Mn-O and Mn-N vibrations were found in Raman spectrum. There is π～π￣* transition, d～π￣* charge-transfer transitions and d～d￣* transitions in electronic spectrum. The current potential curve in acetontrile reveals that Mn(Ⅲ)is in stable valence state.展开更多
The title complex, C22H22MnN5O2, crystallizes in orthorhombic system, space group P212121 with a = 6.887(1), b = 11.718(2), c = 25.721(5) ? V = 2075.7(7) 3, Z = 4, Mr = 443.39, F(000) = 920, Dc = 1.419 g/cm3 and m = 0...The title complex, C22H22MnN5O2, crystallizes in orthorhombic system, space group P212121 with a = 6.887(1), b = 11.718(2), c = 25.721(5) ? V = 2075.7(7) 3, Z = 4, Mr = 443.39, F(000) = 920, Dc = 1.419 g/cm3 and m = 0.665mm-1 (MoKa). The structure was refined to R = 0.0593 and wR = 0.1427 for 3576 observed reflections with I ≥ 2s(I). The Mn(Ⅲ) atom is coordinated to one bzan2- [bzan2- = N, N-ethylenebis(benzoylacetoneiminato)] ligand binding in the equatorial mode and two N3- ions in the axial positions. The azide acts as a trans--(1, 3) bridge, resulting in an infinite helical chain propagating along the b axis.展开更多
A new manganese coordination polymer 1, [Mn（H2O）4（L）]n（ClO4）2n.2nH2O.3nL （L = 2,5-bis（4-pyridyl）-3,4-diaza-2,4-hexadiene）, has been synthesized and structurally characterized. The crystal structure was deter...A new manganese coordination polymer 1, [Mn（H2O）4（L）]n（ClO4）2n.2nH2O.3nL （L = 2,5-bis（4-pyridyl）-3,4-diaza-2,4-hexadiene）, has been synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pn with a = 13.9176（8）, b = 15.4754（9）, c = 15.9670（9） A, β = 99.5010（10）°, V = 3391.8（3） ]k3, Z = 2, C56H68C12MnN16O14, Mr= 1315.10, Dc = 1.288 g/cm^3,μ = 0.344 mm^-1, F（000） = 1374, R = 0.0733 and wR = 0.2035. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,5-bis（4-pyridyl）-3,4-diaza-2,4-hexadiene and four oxygen atoms from water molecules, completing an octahedral geometry. The title complex exhibits a novel supramolecular layer architecture sustained by the concurrence of coordination bonds, hydrogen bonds, and π-π stacking interactions.展开更多
Five manganese complexes of Schiff b ase were synthesized:[Mn Ⅳ,Ⅳ (μ-O)(Salen)] 2 ·DMF ·H 2 O(1),[Mn Ⅳ,Ⅳ (μ-O)(5-BrSalen)] 2 ·DMF ·0.5H 2 O(2),[Mn Ⅳ,Ⅳ (μ-O)]al(1,2-pn)[nr 2 ·H 2 O(3),...Five manganese complexes of Schiff b ase were synthesized:[Mn Ⅳ,Ⅳ (μ-O)(Salen)] 2 ·DMF ·H 2 O(1),[Mn Ⅳ,Ⅳ (μ-O)(5-BrSalen)] 2 ·DMF ·0.5H 2 O(2),[Mn Ⅳ,Ⅳ (μ-O)]al(1,2-pn)[nr 2 ·H 2 O(3),]Mn Ⅳ,Ⅳ (μ-O)[5-Br-Sal(1,2-pn)]r 2 ·H 2 O(4),[Mn Ⅳ,Ⅳ (μ-O)]5-CH 3 -Sal(1,2-pn)5-CH 3 -Sal(1,2-pn)[ 2 ·2H 2 O(5),and were characterized by element analysis,IR and UV-Vis spec tra.The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and s teady high oxide state of manganese.The magnetic properties of1and3have also been studied.The results show t hat there is a weak ferromagneticall y coupling of Mn Ⅳ2 pair at room and low temperature,and the interactions o f complex3are weaker than complex1.展开更多
ive binuclear Mn( Ⅱ ) complexes were synthesized, namely [Mn2LCl]Cl2 .H2O (1) , [Mn2LphCOO] (ClO4 )2 (2) , [Mn2LOH] (ClO4 )2 · C2H5OH (3 ) ,[Mn2LC2H5O](ClO4)2 ·H2O (4) , and [Mn2L(SCN)3] ·2C2H5OH (5) ...ive binuclear Mn( Ⅱ ) complexes were synthesized, namely [Mn2LCl]Cl2 .H2O (1) , [Mn2LphCOO] (ClO4 )2 (2) , [Mn2LOH] (ClO4 )2 · C2H5OH (3 ) ,[Mn2LC2H5O](ClO4)2 ·H2O (4) , and [Mn2L(SCN)3] ·2C2H5OH (5) , where HLis 1 : 2 Schiff bases derived from 1 , 3- diaminopropan-2-ol and picolinaldehyde N- ox-ide. Based on the IR, elemental analyses and conductivity measurement, these com- plexes are proposed to have an endogenous bridge (alkoxide) and an exogenousbridge (it can be an anion). The complexes (3) and (4) were characterized by vari-able temperature magnetic susceptibility (4 300 K) and the data were fitted by theleast-squares to a susceptibility equation derived from the spin Hamiltonian, H =- 2J · S1 · S2. The exchange integral J, was found to be 1. 19 cm-1 for (3) and 1. 06 cm-1 for (4) , indicating that a weak antiferromagnetic exchange is presentin the binuclear Mn( Ⅱ ) complexes.展开更多
文摘The title complex, [Mn2L2(EtOH)2 (bipy )](ClO4)2 (L=N,N'-ethylenebis (1-phenyl-3-imino-1-butanonato), bipy = 4, 4'-bipyridine] crystallizes inmonoclinic system, space group P21/c with a= 12. 63O(5), b=13- 151 (2), c=18. 3773001 reflections The two [MnL(EtOH)]+ units are joined by one 4, 4'-bipyridine molecule to form a centrosymmetric binuclear complex cation [Mn2L2(EtOH)2 (bipy]2+. The coordination geometry around Mn atoms is a distorted octahe-dron with equatorial plane N2O2 from the Schiff base ligand L.
基金supported by Industry High Technology Foundation of Jiangsu (BG2007025)Doctoral Fund from National Ministry of Education (20093227110009),China
文摘A new cyanide-bridged bimetallic assembly [Mn（3-meosalpn）（H2O）]2[Fe（CN）5NO]（1） was obtained by the reaction of [Fe（CN）5NO]2-with [Mn（3-meosalpn）]＋,and characterized by elemental analysis,IR and single-crystal X-ray structure analysis.The complex crystallizes in the monoclinic system,space group P21/c with a = 12.992（5）,b = 13.274（6）,c = 14.644（6） ,β = 115.198（4）o,V = 2285.2（16）3,Z = 2,C43H44FeMn2N10O11,Mr = 1042.61,Dc = 1.515 g/cm3,F（000） = 1072,μ = 0.928 mm-1,S = 1.052,the final R = 0.0347 and wR = 0.0957 for 17377 observed reflections（Ⅰ 〉 2σ（Ⅰ））.X-ray single-crystal diffraction analysis reveals that 1 has a trinuclear molecular structure,in which the two [Mn（3-meosalpn）（H2O）]＋ cations are linked by the central [Fe（CN）5NO]2-anion via two trans CN-groups.Furthermore,the two [Mn（3-meo-salpn）（H2O）]＋ cations and [Fe（CN）5NO]2-anion are connected into a one-dimensional zigzag chain through hydrogen bonding interactions.
基金Project supported by the research grant of Phytochemistry Key Laboratory of Shanxi Province (No. 09JS068)
文摘A new complex [Mn（L）（NCS）]2·0.5CH3CN （H2L = N,N＇-bis（chlorosalicylidene）-1,2-diaminoethane） has been synthesized,and its structure （C70H51Cl8Mn4N13O8S4,Mr = 1833.84） was determined by single-crystal X-ray diffraction analysis. The crystal belongs to the monoclinic system,space group C2/c with a = 25.883（2）,b = 12.3320（13）,c = 13.5951（16） ,β = 112.906（2）,V = 3997.2（7） 3,Z = 2,Dc = 1.524 g/cm3,μ（MoKα） = 1.050mm-1,F（000） = 1852,S = 1.098,the final R = 0.0630 and wR = 0.1847 for 2542 reflections with Ⅰ 〉 2σ（Ⅰ）. The centrosymmetric title complex contains a dimer in which two distorted octahedral Mn（Ⅲ） centers are bridged equatorially by phenolic oxygen of the Schiff base ligand. The units of the complex are linked via weak C-H···N hydrogen bonds,leading to the formation of 1D chains along the b axis. The weak π-π packing interactions and weak intermolecular C（3）-H（3）···N（3） hydrogen bonds stabilize the crystal structure.
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.
文摘The title complex C_(27)H_(26)MnN_5O_2S (M_r= 539. 53 ) crystallizes in monoclinic system, space group P2_1/α with α = 8. 357 (2) A, b = 19. 077 (4) A . c = 16. 267(3) A, β=95. 85(2)°, V=2580(2) A￣3, Z=4, F(000) = 1120, D_c= 1. 39 g/ cm￣3 and μ=0. 601 mm￣(-1)(MoKα). The final R and R_w are 0. 0638 and 0. 0876, respectively. The coordination geometry around Mn atom is a distorted octahedron with a equatorial plane N_2O_2 from the Schiff base ligand bzacen￣(2-), the axial atoms being two nitrogen atoms from a thiocyanate and a pyrimidine ligand. The shifts of v_c=N, v_c=O and v_c=C to lower frequencies in IR and Raman spectra indicate that the ligand bzacen￣(2-) has been coordinated to Mn atom through its nitrogen and oxygen atoms. The lines assigned to Mn-O and Mn-N vibrations were found in Raman spectrum. There is π～π￣* transition, d～π￣* charge-transfer transitions and d～d￣* transitions in electronic spectrum. The current potential curve in acetontrile reveals that Mn(Ⅲ)is in stable valence state.
基金The project (No. 20000168) was supported by the Education Commission of Zhejiang Province
文摘The title complex, C22H22MnN5O2, crystallizes in orthorhombic system, space group P212121 with a = 6.887(1), b = 11.718(2), c = 25.721(5) ? V = 2075.7(7) 3, Z = 4, Mr = 443.39, F(000) = 920, Dc = 1.419 g/cm3 and m = 0.665mm-1 (MoKa). The structure was refined to R = 0.0593 and wR = 0.1427 for 3576 observed reflections with I ≥ 2s(I). The Mn(Ⅲ) atom is coordinated to one bzan2- [bzan2- = N, N-ethylenebis(benzoylacetoneiminato)] ligand binding in the equatorial mode and two N3- ions in the axial positions. The azide acts as a trans--(1, 3) bridge, resulting in an infinite helical chain propagating along the b axis.
基金This work was supported by the Basic Research of Hunan Province (03JZY3036)Science Foundation of Hengyang Normal University (2006A15)Foundation of the Eleventh Five-year Key Constructing Discipline of Hunan Province
文摘A new manganese coordination polymer 1, [Mn（H2O）4（L）]n（ClO4）2n.2nH2O.3nL （L = 2,5-bis（4-pyridyl）-3,4-diaza-2,4-hexadiene）, has been synthesized and structurally characterized. The crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group Pn with a = 13.9176（8）, b = 15.4754（9）, c = 15.9670（9） A, β = 99.5010（10）°, V = 3391.8（3） ]k3, Z = 2, C56H68C12MnN16O14, Mr= 1315.10, Dc = 1.288 g/cm^3,μ = 0.344 mm^-1, F（000） = 1374, R = 0.0733 and wR = 0.2035. In the crystal the manganese atom is six-coordinated by two nitrogen atoms from 2,5-bis（4-pyridyl）-3,4-diaza-2,4-hexadiene and four oxygen atoms from water molecules, completing an octahedral geometry. The title complex exhibits a novel supramolecular layer architecture sustained by the concurrence of coordination bonds, hydrogen bonds, and π-π stacking interactions.
文摘Five manganese complexes of Schiff b ase were synthesized:[Mn Ⅳ,Ⅳ (μ-O)(Salen)] 2 ·DMF ·H 2 O(1),[Mn Ⅳ,Ⅳ (μ-O)(5-BrSalen)] 2 ·DMF ·0.5H 2 O(2),[Mn Ⅳ,Ⅳ (μ-O)]al(1,2-pn)[nr 2 ·H 2 O(3),]Mn Ⅳ,Ⅳ (μ-O)[5-Br-Sal(1,2-pn)]r 2 ·H 2 O(4),[Mn Ⅳ,Ⅳ (μ-O)]5-CH 3 -Sal(1,2-pn)5-CH 3 -Sal(1,2-pn)[ 2 ·2H 2 O(5),and were characterized by element analysis,IR and UV-Vis spec tra.The results of cyclic voltammogram show that Schiff base ligands can drop the potential of manganese and s teady high oxide state of manganese.The magnetic properties of1and3have also been studied.The results show t hat there is a weak ferromagneticall y coupling of Mn Ⅳ2 pair at room and low temperature,and the interactions o f complex3are weaker than complex1.
文摘ive binuclear Mn( Ⅱ ) complexes were synthesized, namely [Mn2LCl]Cl2 .H2O (1) , [Mn2LphCOO] (ClO4 )2 (2) , [Mn2LOH] (ClO4 )2 · C2H5OH (3 ) ,[Mn2LC2H5O](ClO4)2 ·H2O (4) , and [Mn2L(SCN)3] ·2C2H5OH (5) , where HLis 1 : 2 Schiff bases derived from 1 , 3- diaminopropan-2-ol and picolinaldehyde N- ox-ide. Based on the IR, elemental analyses and conductivity measurement, these com- plexes are proposed to have an endogenous bridge (alkoxide) and an exogenousbridge (it can be an anion). The complexes (3) and (4) were characterized by vari-able temperature magnetic susceptibility (4 300 K) and the data were fitted by theleast-squares to a susceptibility equation derived from the spin Hamiltonian, H =- 2J · S1 · S2. The exchange integral J, was found to be 1. 19 cm-1 for (3) and 1. 06 cm-1 for (4) , indicating that a weak antiferromagnetic exchange is presentin the binuclear Mn( Ⅱ ) complexes.
