Synthesis, oxygenation and catalytic performance of manganese complex with p-aminomethyl benzoic acid Schiff base

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.

Hydrothermal Synthesis and Crystal Structure of a Manganese Complex

The title compound [Mn（Phen）（p-MBA）2]n（1） was synthesized via the hydro-thermal reaction of KMnO4 and NaOH with phen and p-methybenzoic acid（p-MBA） in water.The title compound was characterized by elemental analysis and infrared spectra.The crystal of 1 crystallizes in orthorhombic,space group Pbcn with a = 24.132（1）,b = 10.404（0）,c = 9.386（0） ,V = 2356.65（13） 3,Z = 4,C28H22MnN2O4,Mr = 505.42,Dc = 1.424 g/cm3,F（000） = 1044 and μ（MoKα） = 0.598 mm-1.The final R = 0.0781 and wR = 0.1363 for 1972 observed reflections with Ⅰ 〉 2σ（Ⅰ） and R = 0.0897 and wR = 0.1420 for all data.X-ray diffraction reveals that the Phen and p-methy benzoic acid ligand link the Mn atoms into a single one-dimensional coordination polymer,and extensive intermolecular π-π interactions lead these 1D chains to form a two-dimensional supramolecular architecture.

Synthesis and Crystal Structure of a Three-dimensional Manganese(II) Complex (tataH)_2[Mn(pydc)_2]·4H_2O (tata = 2,4,6-Triamino-1,3,5-triazine, pydcH_2 = Pyridine-2,6-dicarboxylic Acid)

A manganese（Ⅱ） complex （tataH）2[Mn（pydc）2]·4H2O （C20H28MBN14O12, Mr = 711.50, tata = 2,4,6-triamino-1,3,5-triazine, pydcH2 = pyridine-2,6-dicarboxylic acid） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1^-, with a = 9.9847（3）, b = 10.9813（3）, c = 15.2616（5）A, a = 101.5310（10）, β = 90.2610（10）, γ = 116.4600（ 10）% V = 1459.44（8）A^3, Z = 2, Dc = 1.619 g/cm^3,μ = 0.539 mm^-1, F（000） = 734, the final R = 0.0292 and wR = 0.0745. In the crystal the Mnn atom is six-coordinated by four carbonyl oxygen atoms and two pyridine nitrogen atoms from two tridentate pydc ligands to furnish a distorted octahedral geometry. The complex shows the A…D…D＇…A＇ H-bonded tetramer. The molecules are packed in a three-dimensional framework structure by the combination of O-H…O, N-H…O and N-H…N hydrogen bonds between （tataH）^＋, [Mn（pydc）2]^2- and crystal water.

Synthesis,Crystal Structure and Magnetic Behavior of a New Manganese(Ⅱ) Coordination Polymer [Mn(DPPZ)(PZDC)(H_2O)] (DPPZ=Dipyrido[3,2-a:2',3'-c]-phenazine and H_2PZDC=Pyrazine-2,3-dicarboxylic Acid)

The title complex, [Mn（DPPZ）（PZDC）（H2O）] 1 （DPPZ = dipyrido[3,2 -a：2＇,3＇- c]phenazine and H2PZDC = pyrazine-2,3-dicarboxylic acid）, has been hydrothermally synthesized and structurally characterized by X-ray single-crystal diffraction, elemental analyses, IR, TG- DTA and magnetic susceptibility measurement. It crystallizes in triclinic, space group P1^- with a = 6.6842（5）, b = 7.5741（6）, c = 20.5755（15）A, α = 90.1160（10）, β = 97.0560（10）, γ = 97.3350（10）°, V= 1025.16（13）A^3, Z = 2, MnC24H14N6O5, Mr= 521.35, Dc= 1.689 g/cm^3, F（000） = 530, μ（MoKa） = 0.699 mm^-1, R = 0.0366 and wR = 0.0810. Compound 1 contains one- dimensional chains which are further stacked through π-π interactions to form a 3D supramolecular architecture. The water molecule O（1W） is involved in hydrogen bonding interactions with symmetric carboxylate oxygen atom 0（4） at （x＋ 1, y＋1, z） and symmetric PZDC nitrogen atom N（6） at （1-x, 1-y, 1-z）, which completes the structure of 1. Magnetic susceptibility measurement indicates that the compound behaves a weak antiferromagnetic exchange interaction.

Synthesis,Crystal Structure and Electrochemical Property of a Dinuclear Manganese(Ⅱ) Complex [Mn_2(C_(12)H_8N_2)_4(C_8H_5O_4)_2](C_8H_4O_4)·H_2O

One dinuclear manganese（II）complex [Mn2（C12H8N2）4（C8H5O4）2]（C8H4O4）·H2O has been synthesized with o-phthalic acid and 1,10-phenanthroline.The crystal structure was determined by X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a = 1.17767（3）,b = 1.22292（2）,c = 1.35860（3）nm,α = 110.5300（10）,β = 97.6140（10）,γ = 93.7300（10）o,V = 1.80307（7）nm3,Dc = 1.404 g/cm3,Z = 2,F（000）= 784,the final GOOF = 1.047,R = 0.0398 and wR = 0.1038.The crystal structure of the title complex consists of one [Mn2（C12H8N2）4（C8H5O4）2]2＋ cation,one uncoordinate o-phthalate anion（C8H4O4）2-and one uncoordinate water molecule.In [Mn2（C12H8N2）4（C8H5O4）2]2＋,the central Mn（II）ion is coordinated by four nitrogen atoms and two oxygen atoms to give a distorted octahedral coordination geometry.The electrochemical property of the title complex was also studied.

Syntheses and Magnetism of μ-1, 3, 5-Benzenetricarboxylato Trinuclear Manganese(Ⅱ) and Nickel(Ⅱ)Complexes

Two new manganese(Ⅱ ) trinuclear complexes and two new nickel (Ⅱ) trinuclear compIexes, namely, [Mn3 (BZT ) (Phen )6] (ClO4 )3 (complex 1 ), [Mn (BZT)· (Nphen )6] (ClO4 )3 (complex 2), [Ni3 (BZT) (Phen)6] (ClO4 )3· 5H2O (complex3) and [Ni3 (BZT ) (Nphen )6] (ClO4 )3 (complex 4 ) (BZT = 1, 3, 5-benzenetricarboxylato, Phen = 1, 10-phenthroline, Nphen = 5-nitro-1, 10-phenanthroline )have been synthesized. The complexes were characterized using elemental analysis,IR and electronic reflection spectra. These complexes are proposed to have extended 1, 3, 5-benzenetricarboxylato-bridged structure and to consist of three manganese (Ⅱ) or three nickel(Ⅱ). The X-band ESR spectra of the complex 1 and complex 2were recorded at room temperature. The variable-temperature magnetic susceptibilities of complex 1 and complex 3 were measured over 4. 2-300 K. According to experimental results of the variable-temperature magnetic susceptibility, the magnetic interaction between the paramagnetic centers is too weak to be detected using the usual magnetic susceptibility technique.

The Paramagnetic 2D Chiral-porous Polymer of L-Phenylalanine and Manganese

Mn(L-Phe)2稨2O]n (Phe=phenylalanine) with a single stranded coordination poly- mer has been synthesized by self-assembly of manganese salt and phenylalanine and characterized by X-ray single-crystal diffraction method. The complex crystallizes in the orthorhombic, space group P212121 with a = 6.0911(1), b = 10.3642(1), c = 30.4321(7) ? V = 1921.16(6) ?, Z = 4, Dc = 1.387 g/cm3, C18H22N2O5Mn, Mr = 401.32, F(000) = 836 and m(MoKa) = 0.717 mm-1. The final R = 0.0614 and wR = 0.1412 for 2291 observed reflections with I > 2s(I). The magnetic behavior study shows that there exist super-exchange antiferromagnetic interactions between the magnetic centers through the effective exchange pathway of the carboxylate group.

SYNTHESIS AND CATALYTIC PROPERTY OF POLYSTYRENE SUPPORTED GLUTAMIC ACID SCHIFF BASE COMPLEX OF Mn(Ⅱ) IN AEROBIC OXIDATION OF CYCLOHEXENE

The polystyrene supported glutamic acid Schiff base complex of Mn （ Ⅱ ） （PS-Sal-Glue-Mn） was prepared with chloromethylated styrene polymer beads, 2,4-dihydroxybenzaldehyde, L-glutamic acid and manganese （ Ⅱ ） acetate tetrahyrate. The polymeric ligand and the complex were characterized by FT-IR, small area X-ray photoelectron spectroscopy （XPS） and 1CP-AES. In the presence of the manganese complex, cyclohexene （1） was effectively oxidized by molecular oxygen without reductant. The major products of the reaction were 2-cyclohexen-l-ol （2）, 2-cyclohexen-l-one （3） and 2-cyclohexen-1- hydroperoxide （4）, which was different with typical oxidation of cyclohexene. The influence of reaction temperature and additive for oxidation had been studied. The selectivity of 2-cyclohexen-1-hydroperoxide varied with reaction time and different additives. The mechanism of cyclohexene oxidation had also been discussed.

溶解性Mn(Ⅱ)配合物活化亚硫酸盐降解有机物的效能和机理研究

亚硫酸盐(S(Ⅳ))对有机废污水几乎没有净化作用,利用可溶性二价锰配合物(Mn(Ⅱ)-NTA(次氮基三乙酸盐))活化S(Ⅳ),并用于氧化降解近中性污染水中的有机污染物,探讨了pH、Mn(Ⅱ)和NTA的投加量和比例、S(Ⅳ)浓度和常见阴离子对Mn(Ⅱ)/NTA/S(Ⅳ)体系氧化降解目标有机污染物(罗丹明B(RhB))效能的影响。实验结果表明,在近中性条件下(pH=6~7.5),氧化降解2μmol/L RhB最适宜的Mn(Ⅱ)、NTA和S(Ⅳ)投加量分别为50、150、500μmol/L,此时RhB在15 min内的总降解率均>85%。紫外可见光谱实验证明中间价态锰(Mn(Ⅲ))的产生及其对S(Ⅳ)活化的关键作用;自由基淬灭实验和电子自旋共振实验证明SO_(4)^(·-)是Mn(Ⅱ)/NTA/S(Ⅳ)体系实现有机污染物快速降解的主要活性氧化物种。

Synthesis and Structural Characterization of Mononuclear Mn^(II) Picolilato Complex Mn(2-C_5H_4NCOO)_2(H_2O)_2.1/2CH_3CN

A Mn(II) picolilato complex Mn(2-C5H4NCOO)2(H2O)2?/2CH3CN 1 has been synthesized. Crystal of 1 is of monoclinic, space group C2/c with a = 25.6613(3), b = 8.6357(2), c = 16.8286(2) ? b = 122.835(1), V = 3133.47(9) ?, Mr=355.7, Dc = 1.508 g/cm3, F(000) = 1456, m = 0.874 cm1 and Z = 8. The final refinement gave R = 0.0362 and wR = 0.1096 for 2264 reflections (I > 2s(I)). The Mn(II) atom possesses distorted octahedral coordination geometry and the structural parameters around the Mn ion are close to those of other Mn analogues. Extensive hydrogen bonding interactions between carboxylate and H2O were observed making one-dimensional chains of the Mn monomers.

Synthesis and Crystal Structure of a Heteronuclear Complex［MnSc（DTPA）（H_2O）_2］·2H_2O

The title complex, [MnSc (DTPA) (H2O)2]·2H2O (DTPA is diethylenetriaminepentaacetic acid). has been synthesized in aqueous solution. Its crystal structure has been determined by four-circle X-ray diffractometer. The crystal is monoclinic with space group P21/n. The cell parameters are as follows:α=0.7886 (3) nm, b=1.5094 (5) nm. c=1. 8162(6) nm; β=100. 32(2)°, V= 2. 121 (2) nm3 , Z= 4 , Dc =1. 75 g/cm3. In the crystal,Sc3+ ion is coordinated by five oxygen atoms and three nitrogen atoms of DTPA with coordination number eight. taking a trigondodecahedron arrangement. Mn2+ ion is coordinated by four oxygen atoms from different DTPA and two oxygen atoms from H2O molecules with coordination number six, forming an octahedron. Each Sc(DTPA) is further connected with Mn2+ ions through four carboxyl groups of DPTA serving as bridges to form a three dimensional network.

饲粮添加氨基酸锰络合物对武冈铜鹅生长性能、屠宰性能和脂质代谢的影响

本试验通过研究饲粮中添加不同水平氨基酸锰络合物对5~10周龄武冈铜鹅生长性能、屠宰性能、器官指数、血清生化指标和肝脏脂质代谢指标的影响,旨在确定其在饲粮中的适宜添加水平。选用28日龄武冈铜鹅300只,随机分为6组,每组5个重复,每个重复10羽(公母各占1/2)。对照组饲喂基础饲粮,各试验组(Ⅰ组~Ⅴ组)分别在基础饲粮中添加20、40、60、80和100 mg/kg的氨基酸锰络合物(以锰元素计)。试验期42 d。结果表明:1)与对照组相比,饲粮添加氨基酸锰络合物对试验鹅生长性能、屠宰性能和器官指数均无显著影响(P>0.05)。2)与对照组相比,Ⅱ组和Ⅲ组血清高密度脂蛋白(HDL)含量显著提高(P<0.05),Ⅱ组~Ⅴ组血清尿酸(UA)含量显著降低(P<0.05)。3)与对照组相比,各试验组肝脏脂肪酸合成酶(FAS)活性均显著提高(P<0.05),Ⅲ组肝脏脂蛋白脂肪酶(LPL)活性显著提高(P<0.05),Ⅰ组~Ⅳ组肝脏乙酰辅酶A羧化酶(ACC)活性显著提高(P<0.05)。4)以肝脏FAS、LPL和ACC活性作为评价指标,通过二次曲线模型估测得出武冈铜鹅饲粮中有机锰适宜添加水平为50.39~53.67 mg/kg。综上可知,饲粮添加氨基酸锰络合物对5~10周龄武冈铜鹅生长性能、屠宰性能和器官指数无显著影响,但适宜水平的有机锰能够改善血清生化指标,调控机体脂质代谢。

Comparison and Relation between Crystal Structures and Magnetic Properties of Two Manganese(Ⅱ)Coordination Polymers Based on(Triazol-1-yl)iso/terephthalic Acid

One new Mn(Ⅱ)coordination polymer,[Mn(Htia)_(2)(H_(2)O)_(2)]_(n)·2nH_(2)O(1,H_(2)tia=4-(1,2,4-triazol-1-yl)isophthalic acid)has been synthesized in mixed solvents under solvothermal conditions.Further characterizations including single-crystal XRD,elemental analysis,IR spectroscopy,thermogravimetric analysis and powder XRD were performed to verify the structure.Complex 1 displays a one-dimensional(1D)chain and is similar to a reported Mn(II)complex 2{[Mn(Htta)_(2)(H_(2)O)_(2)]·2H_(2)O}_(n).It crystallizes in triclinic P1 space group,with a=7.5557(3),b=7.5974(3),c=11.8448(4)Å,α=90.088(1)°,β=95.863(1)°,γ=113.668(1)°,V=618.81(4)Å^(3),Z=1,M_(r)=591.36 g/mol,D_(c)=1.587 mg/m^(3),μ=0.609 mm^(-1),F(000)=303,GOOF=1.062,the final R=0.0359and w R=0.0818 for 4272 observed reflections with I>2σ(I).Based on two similar structures,Hirshfeld surface analysis confirmed both structures are mainly stabilized by O···H/H···O and C···H/H···C hydrogen bonds.Further,weak ferromagnetic behaviors between adjacent Mn(II)ions in 1D chain are obtained.

对甲苯磺酰谷氨酸桥联的一维双链锰配合物的合成、表征与晶体结构

A one-dimensional double-chain coordination polymer [Mn(phen)(tsgluo)] was synthesized in a mixed solution and its crystal structure was determined by X-ray diffraction method. It crystallizes in orthorhombic system with space group P212121. The crystal data are: a=0.530 78(17) nm, b=1.723 9(5) nm, c=2.456 9(8) nm, Z=4, μ=0.729 mm-1, Dc=1.579 g·cm-3, V=2.248 1(12) nm3, R1=0.033 1, ωR2=0.078 9. In the title complex, each Mn(Ⅱ) ion presents a octahedral geometry with the coordination of two nitrogen atoms from 1,10-phenanthroline and four oxygen atoms from three different tsgluo2- ligands. The γ-carboxyl coordinates to Mn(Ⅱ) in the mode of bidentate chelate, while the α-carboxyl coordinates in a bidentate bridging mode. CCDC: 253910.

配合物二(N-质子化亚氨基二乙酸)锰(Ⅱ)的晶体结构

合成了配合物二(N－质子化亚氨基二乙酸)锰(Ⅱ)并于293（2） K用X射线测出了其晶体结构.晶体为四方晶系，空间群为p42_1c， a=0.805 7(1) nm, c=0.955 1(3) nm, V=0.620 0(2)nm3, Z=2, Mr=355.17, Dc=1.902mg/m3, F(000)=366, μ=1.125mm-1.对于465独立反射点［I>2σ(I)］,其R因子为0.019 6,Rw为0.055 3.每个Mn(Ⅱ)与来自四个配体［NH2(CH3COO)2］-中的四个羧基氧原子及两个来自水分子的氧原子配位，形成变形八面体结构.锰（Ⅱ）之间通过桥基配体相联，整个晶体呈层形网状结构，层与层之间通过配体水分子中的氢与未配位的羧基氧、及质子化的氮原子上的氢与未配位的羧基氧之间的氢键相联.

2,2′-联吡啶-3,3′-二羧酸锰(Ⅱ)配合物的合成、晶体结构及性能研究(英文)

以2,2′-联吡啶-3,3′-二羧酸(H2L)和1,10-邻菲啰啉(Phen)为配体合成了一个新的锰(Ⅱ)配合物[Mn(H2O)(L)(Phen)2].(H2O)3。该配合物晶体属单斜晶系,空间群P21/c。在配合物中,中心锰(Ⅱ)离子的配位数是6,处于变形的八面体配位环境中。还测定了标题配合物的磁性,荧光和电化学性能,结果表明:在低温下,配合物有反铁磁性;当激发波长为656 nm时,配合物在682 nm附近有一个宽的荧光发射峰;在循环伏安过程中配合物的电子转移是准可逆的,对应的电极反应是Mn髥/Mn(Ⅱ)。

以2,4′-联苯二羧酸及咪唑并[4,5-f][1,10]邻菲咯啉为配体的钴(Ⅱ)、锰(Ⅱ)配合物的水热合成及晶体结构(英文)

在水热条件下,以2,4′-联苯二羧酸(2,4′-H2bpdc)和咪唑并[4,5-f][1,10]邻菲咯啉(L)为配体构筑了两种配合物{[Co(2,4′-bpdc)(L)(H2O)]·H2O}n(1)和[Mn(2,4′-bpdc)(L)(H2O)]n(2),并利用元素分析、X-射线单晶衍射和热重分析对其结构进行了表征。配合物1具有一维链状结构,配合物2展示了一维双链结构,两个配合物都通过分子间氢键和π-π相互作用形成三维网状结构。

配合物[Mn2(α-Furacrylic radical)4(phen)2(H2O)]·H2O的合成、晶体结构及热稳定性

One novel manganese(Ⅱ) complex [Mn2(α-Furacrylic radical)4(phen)2(H2O)]·H2O with α-furacrylic acid radical and 1,10-phenanthroline has been synthesized and characterized. Crystal data for this complex:monoclinic,space group C2/c,a=1.082 34(16)nm,b=2.445 8(4) nm,c=1.857 4(3) nm,β=104.353(2)°,V=4.763 5(12) nm3,Dc=1.471 g·cm-3,Z=4,F(000)=2 168. Final GooF=1.004,R1=0.039 7,wR2=0.108 7. The crystal structure shows that two neighboring manganese(Ⅱ) ions are linked together by two bridging α-furacrylic acid radicals and one bridging water molecule,forming a cage structure. The Mn(1)…Mn(1A) bond distance is 0.357 6 nm. Each manganese(Ⅱ) ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline molecule and four oxygen atoms from three α-furacrylic acid radicals and one water molecule,forming distorted octahedral coordination geometry. Thermal stability of the complex was also discussed.

复杂含钴物料处理工艺研究

针对含锰19%、钴8%的复杂硫化物物料进行了试验研究,确定采用"预浸脱锰—硫酸化焙烧—浸出—萃取"工艺流程。在预浸脱锰过程中,通过采用两段逆流浸出,可有效降低钴的浸出率,提高溶液中锰含量,锰的浸出率可达到85%以上,溶液可蒸发结晶生产硫酸锰或直接沉淀生产碳酸锰。脱锰后渣进行了硫酸化焙烧试验研究,考察了焙烧温度、反应时间等因素对钴浸出率的影响,经硫酸化焙烧后,钴的浸出率可达到95%以上。

2, 6-二氯苯甲酸桥联的双核锰配合物的水热合成与晶体结构(英文)

A dinuclear manganese(Ⅱ) complex, [Mn2(L1)2(phen)4]·(ClO4)2 (1), has been synthesized and structurally characterized (HL1=2,6-dichlorobenzoic acid, phen=1,10-phenanthroline). It crystallizes in triclinic system, space group P1 with a=1.112 3(4) nm, b=1.378 2(4) nm, c=2.085 7(3) nm, α=93.768(2)°, β=90.606(10)°, γ=95.606(3)°, V=3.174 8(15) nm3, Z=2, C62H38Cl6Mn2N8O12, Mr=1 409.58, Dc=1.475 g·cm-3, μ=0.718 mm-1, F(000)=1 428, R=0.064 3, wR=0.138 3. In the crystal the manganese atom is six-coordinated by two oxygen atoms from two different 2,6-dichlorobenzolate molecules and four nitrogen atoms from two 1,10-phenanthroline molecules, completing an octahedral geometry. CCDC: 692296.