Synthesis, Crystal Structure and Thermal Property of a Manganese(II) 4-Carboxyphenoxyacetate Complex

The manganese(II) complex, [Mn(phen)2(4-CPOA)(H2O)]?5H2O (4-CPOAH2 = 4- carboxyphenoxyacetic acid) has been synthesized and characterized by elemental analyses, IR, TG and single-crystal X-ray diffraction. The crystal is of monoclinic, space group C2/c, with a = 27.471(3), b = 18.490(4), c = 14.507(3) ?, β = 115.13(3)o, V = 6671(3) ?3, Z = 8, Mr = 717.58, Dc= 1.429 g/cm3, μ = 0.462 mm–1, F(000) = 2984, the final R = 0.0535 and wR = 0.1200 for 5413 observed reflections with I > 2σ(I). The Mn(II) atom is coordinated by one O atom of 4-carboxy- phenoxyacetate, four N atoms of two 1,10-phenanthroline and one water molecule, residing in a distorted octahedral environment. A supramolecular network structure is formed by hydrogen bonds and π-π stacking interactions.

Synthesis of α-Naphthol and 2,4,7-Trimethyl-Quinolin-5-ol by Using Manganese (III) Acetate and Analysis of Its Antimicrobial Properties

This study involves the aromatization reactions of some ketone derivatives through Manganese (III) acetate. The ketone derivatives used in the study are α-tetralone (1a), 2,4,7-trimethyl-7,8-dihydro quinolinone (1b). At the end of the aromatization reactions of these ketone derivatives the synthesized structures of α-naphthol (2a), 2,4,7-trimethylquinoline-5-ol (2b) were identified by spectroscopic methods such as IR, 1H-NMR, 13C-NMR, FAB-MS respectively. Micro-organism types such as Escherichia coli, ATCC 25922, Klepsiella pneumoniae, Staphylococcus aureus NRRL B767, Salmonella typhimurium NRRLB 4420, Bacillus subtilis NRS 744, Bacillus cereus ATCC 11778, Micrococcus luteus ATCC-9341, Listeria monoaytopenus ATCC-7644 bacteria and yeast fungus Candida albicans were used to study the anti-microbial properties of the synthesized 2b compound. The obtained results have determined that compound number 2b has a good antibacterial impact on Bacillus subtilis (NRS-744).

Ethyl and butyl acetate oxidation over manganese oxides

Mangenese oxides were synthesized using two new methods,a novel solvent‐free reaction and a reflux technique,that produced cryptomelane‐type products(K‐OMS‐2).Oxides were also synthesized using conventional methods and all specimens were applied to the oxidation of ethyl acetate and butyl acetate,acting as models for the volatile organic compounds found in industrial emissions.The catalysts were also characterized using N2adsorption,X‐ray diffraction,scanning electron microscopy,temperature programmed reduction and X‐ray photoelectron spectroscopy.Each of the manganese oxides was found to be very active during the oxidation of both esters to CO2,and the synthesis methodology evidently had a significant impact on catalytic performance.The K‐OMS‐2nanorods synthesized by the solvent‐free method showed higher activity than K‐OMS‐2materials prepared by the reflux technique,and samples with cryptomelane were more active than those prepared by the conventional methods.The catalyst with the highest performance also exhibited good stability and allowed90%conversion of ethyl and butyl acetate to CO2at213and202°C,respectively.Significant differences in the catalyst performance were observed,clearly indicating that K‐OMS‐2nanorods prepared by the solvent‐free reaction were better catalysts for the selected VOC oxidations than the mixtures of manganese oxides traditionally obtained with conventional synthesis methods.The superior performance of the K‐OMS‐2catalysts might be related to the increased average oxidation state of the manganese in these structures.Significant correlations between the catalytic performance and the surface chemical properties were also identified,hig-hlighting the K‐OMS‐2properties associated with the enhanced catalytic performance of the materials.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.

Reaction of Phenylethyne with 2,4-Pentanedione in the Presence of Manganese(Ⅲ) Acetate and Oxygen

The reaction of phenylethyne with 2,4-pentanedione in the presence of manganese(Ⅲ) acetate and oxygen at room tempraure gave 4-acetyl-5-benzoyl-3-methyl-1, 2-dioxolan-3-ol, 2-acetyl-3-benzoloxirane and 3-acety-2-methyl-phenylfuran

Synthesis and Crystal Structure of Tetrakis(1-vinylimidazole-kN^3)diisothiocyanatomanganese(II)

The title compound I （C22H24MnN10S2, Mr = 547.57） has been synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the monoclinic system, space group P2 1/c with a = 8.6010（17）, b = 9.0180（18）, c = 17.773（4）A, β = 101.79（3）°, V = 1349.5（5）A^3, Z = 2, Dc = 1.348 g/cm^3,/1 = 0.674 mm^-1, F（000） = 566, the final R = 0.0488 and wR = 0.1289. In the structure, each Mn atom is coordinated by four Vim （Vim = 1-vinylimidazole） ligands and a pair of monodentate isothioeyanic groups, affording a compressed oetahedral MnN6 core.

Synthesis and Crystal Structure of a Novel Tetranuclear Manganese(II) Complex with a Tripodal Peptide Ligand

The title complex, [Mn2(O-Py3A)(DPK-CH3O)(CH3OH)]2?2ClO4?4CH3OH (C64H70Cl2- Mn4N12O22, Py3AH = N-(bis(2?-pyridyl)methyl)-2-pyridinecarboxamide, DPK = di-2-pyridyl ketone) has been synthesized and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 12.667(9), b = 16.793(12), c = 17.070(13) ?, β = 100.997(13)o, V = 3565(5) ?3, Dc = 1.537 g/cm3, Mr = 1649.98, Z = 2, μ(MoKα) = 0.851 mm-1 and F(000) = 1696. The final R and wR are 0.0639 and 0.1320, respectively for 3979 observed reflec- tions with I > 2σ(I). In the tetranuclear complex, each Mn(II) atom is six-coordinated and the four Mn(II) atoms are coplanar, exhibiting a parallelogram arrangement; while the deprotonated ligands are oxidized to O-Py3A2- anions and cleaved to DPK-CH3O– anions (the monoanion of mono- methylated diol of DPK) furthermore.

Preparation, Characterization, and Application of Manganese Oxide Coated Zeolite as Adsorbent for Removal of Copper(II) Ions from Seawater

The present study is aimed to examine the adsorption characteristics of Cu(II) by using the novel cellulose acetate composite and to apply it for the removal of Cu(II) from real wastewater samples. In order to achieve this objective, ethylenediamine, diethylenetriamine, triethylenetetramine and te-traethylenepentanene were used for immobilization of grafted cellulose acetate-nanoscale manganese dioxide. Cellulose was extracted from mangrove species Avicennia marina and converted to cellulose acetate then it was formed composite with nano-manganese dioxide via precipitation of nano-manganese dioxide on it. The composite was grafted with acrylamide monomer before immobilization. The synthesized compounds were used for adsorption of Cu(II) and characterized by FT-IR, TGA and SEM. The adsorption characteristics of synthesized sorbents were optimized. Langmuir and Freundlich models were used to establish sorption equilibria. The analytical applications of these modified materials were applied successfully for the removal of Cu(II).

Synthesis, Crystal Structure and Spectrum Properties of Trinuclear Manganese Coordination Compound Mn_3(2,2'-bipy)_2(3,5-DMBA)_6

A novel complex Mn3（2,2＇-bipy）ff3,5-DMBA）6 with 3,5-dimethylbenzoic acid （3,5-DMBA） and 2,2＇-bipyridine （2,2＇-bipy） has been synthesized by means of a solvent method. It crystallizes in the monoclinic space group C2/c with a = 3.1118（6）, b = 1.1754（2）, c = 2.0887（4） nm, β = 118.50（3）°, V= 6.714（2） nm3, Dc = 1.384 g/cm3, Z = 8, F（000） = 2912, the final GOOF = 1.078, R = 0.0691 and wR = 0.1455. The crystal structure shows that the three coordinated manganese（II） ions lie in a line with the middle one as the symmetric center. The distance between the central manganese（II） and the symmetric one is 0.3549 nm. There exist two coordination modes for the three manganese （II） ions： the symmetric manganese（II） ions are coordinated with three oxygen atoms and two nitrogen atoms from three 3,5-DMBA molecules and one 2,2＇-bipy molecule, respectively, forming a distorted square-pyramidal coordination geometry; the middle manganese（II） ion is coordinated with six oxygen atoms from six 3,5-DMBA molecules, generating a distorted octahedral coordination geometry. Spectrum properties of the complex were also studied.

A Novel Two-dimensional Lead(Ⅱ) Coordination Polymer Based on Dinuclear Lead(Ⅱ) Unit Containing(5-Chloro-quinolin-8-yloxy) Acetate

A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603（7）, b = 8.6907（4）, c = 8.4745（3）A, β = 101.1110（11）°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25（9）A3, Z = 4, Dc = 2.628 g/cm^3, F（000） = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead（II） cation, one（5-chloro-quinolin-8-yloxy）acetate（L） ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit（SBU） and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079（1）A. The fluorescence emission peak of complex 1 appears near 407 nm.

Hydrothermal Synthesis and Crystal Structure of a Manganese(Ⅱ) Complex:Mn_(1.5)(cbba)_3(phen)

A new metal-organic complex Mn1.5（cbba）3（phen）（Hcbba = 2-（4＇-chlorine-ben-zoyl）benzoic acid,phen = 1,10-phenanthroline） 1 has been hydrothermally synthesized and struc-turally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectro-scopy.The compound crystallizes in triclinic,space group P1 with a = 12.137（2）,b = 14.535（3）,c = 14.894（3）,α = 86.380（3）,β = 70.381（3）,γ = 72.647（3）°,V = 2360.3（8）3,C107H64Cl6Mn3N4O18,Mr = 2071.14,Dc = 1.457 g/cm3,μ（MoKα） = 0.638 mm-1,F（000） = 1055,Z = 1,the final R = 0.0638 and wR = 0.1905 for 6155 observed reflections（I 2σ（I））.It exhibits a 3D supramolecular network through hydrogen bonding and π-π stacking interactions.

Synthesis and Structure of a New Dimanganese Complex [Mn_2(μ-OAc)_2(phen)_4](ClO_4)_2

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.

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.

Synthesis and Structure of the Manganese Complexwith 2-Aminopyridine N-oxide

The complex Mn(apo)6Cl2 (apo=2-aminopyridine N-oxide) was obtained by the reaction of MnCl2(4H2O with apo(HCl and NaOH in ethanol. A single-crystal X-ray study shows that the complex is mononuclear with octahedral coordination environment (MnC30H36N12O6Cl2). The oxygen atoms from apo ligands coordinate to the manganese atom forming Mn(apo)6Cl2. The compound Mn(apo)6Cl2 is hexagonally symmetric with space group R3, lattice constants: a = 12.010(2), b = 12.010(2), c = 20.232(4) ?, ( = 120(, V= 2527.4(7) ?3, Z=3, Mr =786.55, Dc=1.550 g/cm3, (= 0.614mm-1, F(000) = 1221, R = 0.0541, Rw = 0.0580 for 1229 reflections with I>2((I). The distances between Mn(II) and O atoms are in the range from 2.171(5) to 2.184(5) ?, and the distance between the chlorine anion and N atom of amido group is 3.3 ?. The dihedral angle between two adjacent pyridine ring planes is 59.19 (0.17)°.

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.

Investigation of suitable precursors for manganese oxide catalysts in ethyl acetate oxidation

The control of ethyl acetate emissions from fermentation and extraction processes in the pharmaceutical industry is of great importance to the environment.We have developed three Mn_(2)O_(3)catalysts by using different Mn precursors(MnCl_(2),Mn(CH_(3)COO)_(2),MnSO_(4)),named as Mn_(2)O_(3)-Cl,-Ac,-SO_(4).The tested catalytic activity results showed a sequence with Mn precursors as:Mn_(2)O_(3)-Cl>Mn_(2)O_(3)-Ac>Mn_(2)O_(3)-SO_(4).The Mn_(2)O_(3)-Cl catalyst reached a complete ethyl acetate conversion at 212℃(75℃lower than that of Mn_(2)O_(3)-SO_(4)),and this high activity 100%could be maintained high at 212℃for at least 100 hr.The characterization data about the physical properties of catalysts did not show an obvious correlation between the structure and morphology of Mn_(2)O_(3)catalysts and catalytic performance,neither was the surface area the determining factor for catalytic activity in the ethyl acetate oxidation.Here we firstly found there is a close linear relationship between the catalytic activity and the amount of lattice oxygen species in the ethyl acetate oxidation,indicating that lattice oxygen species were essential for excellent catalytic activity.Through H_(2)temperature-programmed reduction(H_(2)-TPR)results,we found that the lowest initial reduction temperature over the Mn_(2)O_(3)-Cl had stronger oxygen mobility,thus more oxygen species participated in the oxidation reaction,resulting in the highest catalytic performance.With convenient preparation,high efficiency,and stability,Mn_(2)O_(3)prepared with MnCl_(2)will be a promising catalyst for removing ethyl acetate in practical application.

Manganese(Ⅲ) acetate-mediated radical reaction of [60]fullerene with bromoacetic acid,3-chloropropionic acid or 1-naphthylacetic acid

The manganese(Ⅲ) acetate-mediated radical reaction of [60]fullerene (C60) with three carboxylic acids,that is,bromoacetic acid,3-chloropropionic acid,and 1-naphthylacetic acid,was investigated. The reaction of C60 with bromoacetic acid in the presence of 4-(dimethylamino)pyridine afforded the anticipated C60-fused lactone,while the reaction with 3-chloropropionic acid unexpectedly led to the formation of a novel C60-fused lactone with the loss of one molecule of HCl. Interestingly,the reaction with 1-naphthylacetic acid under similar conditions gave both C60-fused lactone and 1,4-adduct,yet each of them could be selectively obtained by controlling reaction conditions. It was also observed that the C60-fused lactone bearing a bulky naphthyl group existed as two isomers.

基于NSGA-II的醋酸甲酯水解工艺经济优化控制

针对PTA生产系统中副产物醋酸甲酯水解工艺,研究基于最小经济成本的集成优化与厂级动态控制。首先根据醋酸甲酯水解工艺动力学机理模型,建立Aspen稳态模拟系统,采用灵敏度分析计算待优化变量的可行域,建立经济优化总成本目标函数;然后将模型计算和过程模拟相结合,利用NSGA-II算法寻找较优的反应精馏塔各操作参数,实现最小经济成本;最后依据最优的经济优化结构和操作参数,设计厂级动态控制系统,施加醋酸甲酯进料与流量扰动,其动态响应的结果验证了上述控制方案可以有效抑制扰动下的塔内各变量和产品成分变化,确保生产安全平稳运行。

Manganese (Ⅲ) Acetate:A Versatile Reagent in Organic Chemistry

1 Results Free radical reactions have become increasingly important,as well as a very attractive tool,in organic synthesis within the last two decades,due to their powerful,selective,specific,and mild reaction abilities.Mn(OAc)3 mediated oxidative free radical reactions have been extensively developed in the last twenty years[1,6].Numerous regio-,chemo-,and stereoselective synthetic methods have been developed in both inter-and intramolecular reactions,and have detailed the progress of Mn(OAc)3 mediated...

A 3-D Metal-organic Framework Mn(II) Complex with Ant Net Constructed from 3-Pyridin-4-yl-benzoic Acid

A new coordination polymer, [Mn(3,4-pybz)2]n·3(H2O)(1), has been hydrothermally synthesized from Mn Cl2·4H2O and an unsymmetrical 3-pyridin-4-yl-benzoic acid(3,4-Hpybz), and characterized by IR, elemental analysis, thermogravimetric analysis, and singlecrystal X-ray diffraction. In complex 1, each 3,4-pybz ligand represents a three-connected node to combine with the six-connected Mn(II) ions, generating a 3D binodal(3,6)-connected ant network. In addition, magnetic investigations reveal that complex 1 exhibits an antiferromagnetic behavior. According to the crystal structure, the full-geometrical optimization of complex 1 was carried out by using hybrid DFT methods at the B3LYP/6-31G(d) level. Meantime, the DFT-BS approach was applied to study the magnetic coupling behavior for complex 1, and the result reveals that the calculated exchange coupling constants J were in good agreement with the experimental data.

Samarium(II) Diiodide Induced Polarity Inversion of π-Allyl Palladium Complexes: The Formation of Allylic Selenides

Allylic acetates were reduced with Pd(0)-SmI2 in the presence of ArSeBr to form corresponding allylic selenides in good yields.