Kristallstrukturen von Verbindungen A2[MnF3(SO4)] (A = Rb,NH4, Cs): Jahn‐Teller‐Ordnung in Mangan(III)‐fluoridsulfaten. I.

Jahn‐Teller Ordering in Manganese(III) Fluoride Sulphates. I. Crystal Structures of A₂[MnF₃(SO₄)] (A = Rb, NH4, Cs) The three isostructural fluorosulphatomanganates(III) A₂[MnF₃(SO₄)] (A = Rb, NH₄, Cs) crystallize in space group P2₁/c, Z = 4. Rb₂[MnF₃(SO₄)]: a = 7.271, b = 11.091, c = 8.776Å, β = 92.26°, R = 0.033; (NH₄)₂[MnF₃(SO₄)]: a = 7.299, b = 10.157, c = 8.813Å, β = 91.51°, R = 0.025; Cs₂[MnF₃(SO₄)]: a = 7.365, b = 11.611, c = 9.211, β = 92.30°, R = 0.029. In the chain anions [MnF₃(SO₄)]^2— manganese(III) is coordinated by two trans‐terminal and two trans‐bridging fluorine ligands, and by the O‐atoms of two briding sulphate ligands in trans position. The Jahn‐Teller effect induces a variety of antiferrodistortive ordering resulting in distorted [MnF₄O₂] octahedra with alternating elongation of F—Mn—F — and O—Mn—O — axes, respectively. Thus, only asymmetrical bridges are formed.     

Synthese und Struktur einer tetragonalen Fluorperowskitvariante mit Kationendefizit — Cs4PdMn2F12

Synthesis and Structure of a Tetragonal Fluoroperovskitevariety Deficient in Cations — Cs₄PdMn₂F₁₂ Single crystals of red Cs₄PdMn₂F₁₂ were obtained by systematic investigations in the system CsF/MnF₃/Pd/PdF₃. The Compound crystallizes with a = b = 856.89(6) pm, c = 1918.35(18) pm, spcgr. I 4₁lamd — D (No. 141) and Z = 4. It is structurally related to K₄MnMn₂F₁₂, but with square arrangement (isotypic?) of F^— around Pd²⁺.     

脯氨酸衍生的胺基吡啶四氮锰配合物催化双氧水参与的烯烃不对称环氧化反应（英文）

自然界中存在许多的金属酶,它们参与促进各种各样的氧化反应,例如羟化反应,环氧化反应等.金属酶催化的反应具有催化效率高、反应条件温和、选择性高等优点.受大自然中的金属酶结构及其性质的启发,人们提出了仿生催化氧化的理念,并开始对金属酶进行模拟,致力于发展清洁氧化的反应方式.在过去的几十年中,科学家们设计合成了一系列仿生金属配合物催化剂.例如,利用非手性的乙二胺骨架设计合成出四齿氮配体MEP(N,N'-dimethylN,N'-bis(2-pyridinylmethyl)ethane-1,2-diamine),将其制备成相应的铁配合物催化剂,该铁催化剂可以很好的实现脂肪族烯烃的环氧化,产率高达90%.2003年,Stack小组首次报道了利用手性N,N-二甲基环己二胺骨架衍生的四齿氮配体金属配合物Mn-MCP-(OTf)2(MCP=N,N-dimethyl-N,N-bis(2-pyridylmethyl)cyclohexane-trans-1,2-diamine)催化的不对称环氧化反应.该反应的对映选择性仅仅为10%.因此,发展新型手性四氮配体金属配合物,用于高产率、高对映选择性的不对称环氧化反应,值得进行深入研究.近年来发展的一些含手性二胺骨架的四齿氮配体,例如PDP(2-[[2-(1-(pyridin-2-ylmethyl)-pyrrolidin-2-yl)pyrrolidin-1-yl]methyl]pyridine),被应用到不对称环氧化反应中,但是其手性二胺骨架为联吡咯,价格昂贵,难以制备.这在很大程度上限制了其在不对称合成中的实际应用.因此,利用一些易于合成的手性二胺骨架,发展结构新颖、催化性能优良的四氮金属配合物,成为实现高效、高选择性不对称环氧化反应的关键.在之前的工作基础上,本文以简单易得、价格低廉的天然氨基酸——L-脯氨酸为起始原料,选取吡啶环和含取代基的吡啶环作为侧基氮供体,制备了三种手性四齿氮配体.随后,我们利用新发展的手性四齿氮配体,合成了相应的锰配合物,并且分别将其运用于烯烃不对称环氧化反应中,仔细评估了这些锰金属配合物的催化性能.建立了以0.2 mol%的锰配合物为催化剂,0.5当量的2,2-二甲基丁酸为添加剂,30%双氧水为氧化剂,反应温度为–30 oC,乙腈为溶剂的催化不对称环氧化反应体系.反应结果显示:该催化剂催化的不对称环氧化反应底物适用性广泛,其中苯乙烯、苯并吡喃、烯酰胺等化合物均可以被成功地转化为相应的环氧化物,得到中等至优异的对映选择性(产率最高可达95%,对映选择性最高可达99%).     

硝化后熔融制样法——X射线荧光光谱同时测定锰矿中主、次元素

采用X射线荧光光谱法同时测定锰矿中Mn,SiO₂,Fe,P,Al₂O₃,CaO,MgO和S等8个组分。因锰矿熔融制样过程中产生气泡现象严重,影响到测定的准确性和重现性,文章提出了先加硝酸破坏锰矿样品中的有机物,然后用12∶22混合熔剂在1 000 ℃熔融制样的方法,解决了锰矿熔融制样过程中有机物挥发产生大量的气泡导致熔剂飞溅的问题,消除了试样的粒度效应和矿物效应,同时也解决了硫元素在制样过程中容易挥发的难题。对熔剂、熔融时间、硝酸加入量等制样条件进行了选择,并采用可变理论α系数法校正基体的吸收增强效应,扩大了测定线形范围,进行了方法的精密度及准确度试验。与化学法对比,本法测定锰矿中各组分的定量分析结果令人满意,方法准确、快速、简便。     

食品分析中微量元素铁,锰,锌,铜快速分光光度测定法的研究

铁、锰、锌、铜的快速分析常用原子吸收光度法、发射光谱法、等离子体法、电位溶出法等。本文则研究了快速分光光度法，提出了新的分析方法及若干试验研究结果。     

Ferrocene-Mn π-interaction in the complex [Fc2Bpz2Mn(THF)Cl]

The ferrocene-based bis(pyrazol-1-yl)borate ligands [Fc₂Bpz₂]⁻ ([2]⁻) and [Fc₂Bpz^Ph₂]⁻ ([2^Ph]⁻) have been prepared (Fc: ferrocenyl; pz: pyrazol-1-yl; pz^Ph: 3-phenylpyrazol-1-yl). Treatment of [2]⁻ and [2^Ph]⁻ with MnCl₂ in THF leads to the complexes [Fc₂Bpz₂Mn(THF)(μ-Cl)₂Mn(THF)pz₂BFc₂] (3) and [Fc₂Bpz^Ph₂Mn(THF)Cl] (3^Ph), respectively, which have been structurally characterized by X-ray crystallography. While there is clearly no ferrocene-Mn^II π-coordination in the solid-state structure of 3, short Mn^II-C₅H₄ contacts are established in 3^Ph (shortest Mn-C distances: 2.780(2) Å, 2.872(2) Å). The cyclic voltammograms of K[2^Ph] and 3^Ph show the first ferrocene/ferricinium redox wave of 3^Ph to be shifted anodically by 0.60 V compared with the first Fe^II/Fe^III transition of K[2^Ph].     

流动注射在线离子交换预富集火焰原子吸收光谱法测定水样中微量锰

提出了以732强酸型阳离子树脂作填充材料,流动注射在线离子交换预富集火焰原子吸收光谱法测定水样中微量锰的分析方法。优化了各项化学条件和流路参数等,考察了共存离子的干扰。富集倍数可达24倍,分析速度为15～20样/h,检出限为2.0ng/mL,相对标准偏差为2.8%(n=15)。对雨水加标回收,回收率为97%～103%。     

Synthesis, characterisation and catalytic activities of manganese(III) complexes of pyridoxal-based ONNO donor tetradenatate ligands

Reaction of Mn^II(CH₃COO)₂ with dibasic tetradentate ligands, N,N′-ethylenebis(pyridoxylideneiminato) (H₂pydx-en, I), N,N′-propylenebis(pyridoxylideneiminato) (H₂pydx-1,3-pn, II) and 1-methyl-N,N′-ethylenebis(pyridoxylideneiminato) (H₂pydx-1,2-pn, III) followed by aerial oxidation in the presence of LiCl gives complexes [Mn^III(pydx-en)Cl(H₂O)] (1) [Mn^III(pydx-1,3-pn)Cl(CH₃OH)] (2) and [Mn^III(pydx-1,2-pn)Cl(H₂O)] (3), respectively. Crystal and molecular structures of [Mn(pydx-en)Cl(H₂O)] (1) and [Mn(pydx-1,3-pn)Cl(CH₃OH)] (2) confirm their octahedral geometry and the coordination of ligands through ONNO(2-) form. Reaction of manganese(II)-exchanged zeolite-Y with these ligands in refluxing methanol followed by aerial oxidation in the presence of NaCl leads to the formation of the corresponding zeolite-Y encapsulated complexes, abbreviated herein as [Mn^III(pydx-en)]-Y (4), [Mn^III(pydx-1,3-pn)]-Y (5) and [Mn^III(pydx-1,2-pn)]-Y (6). These encapsulated complexes are used as catalysts for the oxidation, by H₂O₂, of methyl phenyl sulfide, styrene and benzoin efficiently. Oxidation of methyl phenyl sulfide under the optimized reaction conditions gave ca. 86% conversion with two major products methyl phenyl sulfoxide and methyl phenyl sulfone in the ca. 70% and 30% selectivity, respectively. Oxidation of styrene catalyzed by these complexes gave at least five products namely styrene oxide, benzaldehyde, benzoic acid, 1-phenylethane-1,2-diol and phenylacetaldehyde with a maximum of 76.9% conversion of styrene by 4, 76.3% by 5 and 76.0% by 6 under optimized conditions. The selectivity of the obtained products followed the order: benzaldehyde > benzoic acid > styrene oxide > phenylacetaldehyde > 1-phenylethane-1,2-diol. Similarly, ca. 93% conversion of benzoin was obtained by these catalysts, where the selectivity of the products followed the order benzil > benzoic acid > benzaldehyde-dimethylacetal. Tests for the recyclability and heterogeneity of the reactions have also been carried. Neat complexes are equally active. However, the recycle ability of encapsulated complexes makes them better over neat ones.     

二氧化锰/球形活性炭复合材料在有机系超级电容器中的应用

以Mn(NO3)2和中间相炭微球基球形活性炭（MSAC）为原料,采用热分解的方法成功制备了一种新型超级电容器用MnO2/MSAC球形复合材料。 通过X射线衍射、扫描电子显微镜和透射电子显微镜对比分析了该复合材料的结构和形貌,并采用循环伏安、恒流充放电、电化学阻抗（EIS）、循环充放电研究了电极的电化学性能。 结果表明,MnO2/MSAC球形复合物中的MnO2粒径为100~160 nm;在1 mol/L的LiPF6/(DMC+EC)（EC：乙烯碳酸酯;DMC：碳酸二甲酯) 有机电解液中MnO2/MSAC复合材料所组装的电容器的工作电压可达3.0 V,在0.002 A/cm2电流密度下,MnO2/MSAC球形复合材料的电容器和单纯MSAC材料的电容器的首次循环比容量分别为186和167 F/g,在循环过程中,MnO2/MSAC球形复合材料的电容器循环200次后充放电的库仑效率基本保持在95%以上。 此外,MnO2/MSAC球形复合材料的充放电曲线表现出典型的电容行为;循环伏安曲线也表现出良好矩型特征,同时具有较高的能量密度和良好的功率性能。     

锌锰元素对男性性功能障碍的双向治疗作用

对男性性功能障碍诸如阳痿、阳强症，以临床实例为据，用中西两种医学理论为指导，突出分析微量元素锌、锰的治疗作用，初步验证出锌锰元素在治疗阳痿、阳强这类病证，在对交感神经和副交感神经调控方面有着双向治疗作用。