Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Dimeric Manganese-Catalyzed Hydroarylation and Hydroalkenylation of Unsaturated Amides

An unprecedented Mn(I)-catalyzed selective hydroarylation and hydroalkenylation of unsaturated amides with commercially available organic boronic acids is reported. Alkenyl boronic acids have been successfully employed for the first time in Mn(I)-catalyzed carbon–carbon bond formation. A wide array of β-alkenylated amide products can be obtained in moderate to good yields, which offers practical access to five- and six-membered lactams. This protocol has predictable regio- and chemoselectivity, excellent functional group compatibility and ease of operation in air, representing a significant step-forward towards manganese-catalyzed C−C coupling.     

β-MnO2高压相的从头计算模拟

 基于密度泛函理论（DFT），用完全势能线性缀加平面波方法（FPLAPW）计算模拟了MnO₂的同质多相变体（金红石型结构、CaCl₂型结构、黄铁矿型结构），通过计算，预测了β-MnO₂在5 GPa时从金红石型结构转变为CaCl₂型结构，在20 GPa时进一步转变为黄铁矿型结构。另外，还总结和比较了几种金红石型结构二氧化物的压致相变特点，得出第Ⅳ主族元素的金红石型结构氧化物有很好的规律性，发生的相变序列基本一致；并随着金属阳离子半径的增大，发生相变的压力值也相应地递减，各氧化物的体积模量值相应地减小。     

Hydrothermal Synthesis and Structure of [Mn(C_8H_5NO_4)·H_2O]_n·2nH_2O

1 INTRODUCTION The self-assembly of organic-inorganic hybrid ma- terials is an intriguing area, which is yielding new generations of supramolecular architectures[1, 2]. Coor- dination by transition metals with multifunctional ligands is one of the main design principles. As a rigid multi-dentate ligand, 5-aminoisophthalic acid (AIP) has received considerable attention owing to the variety of bridging abilities[3~8]. It can engage in three types of intermolecular interactions: (1) M-L b…     

Fluorous osmium tetraoxide (OsO4): a recoverable and reusable catalyst for dihydroxylation of olefins

A fluorous osmium catalyst was firstly developed. It had been effectively used as recoverable and reusable catalyst in the dihydroxylation of olefins.     

Manganese(II) complexes with diethylamine in aqueous solutions

Interaction between MnCl₂ and diethylamine (DEA) in aqueous solutions has been studied by UV, IR, and EPR spectroscopy as part of the design and research program on models of natural photosystems. The composition of the precipitate for comparable concentrations of reagents and solute oxygen has been investigated. Mn(II) was found to be oxidized with oxygen to give MnO₂·H₂O as a precipitate. In the solution over the precipitate, Mn(III) complexes with DEA are formed; the complex molecule has four and six amine molecules in the coordination sphere.     

微分脉冲溶出伏安法同时测定食品中的锌铁锰

在1％乙二胺-0．1mol／L酒石酸钠-pH11．82 Britton—Robinson缓冲溶液体系中用微分脉冲溶出伏安法同时测定锌、铁、锰三种微量元素。它们的峰电位分别为-1184，-1392和-1456mV(vs．Ag/AgCl)；线性范围分别为：0.001—0.015，0．005—0．05和0．04—0．7μg／mL，最低检出浓度分别为0．0007，0．0014和0．0193μg／mL。本法操作简便、准确、灵敏度较高，用于食品中这三种元素的分析，结果令人满意。     

Synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine and (±)-convolutamydines A and E, through enolization-Claisen rearrangement of 2-allyloxyindolin-3-ones

Claisen rearrangement triggered by enolization of 2-allyloxyindolin-3-ones with DBU was performed in order to prepare 3-allyl-3-hydroxyindolin-2-ones. Total synthesis of 3-hydroxyindolin-2-one alkaloids, (±)-donaxaridine, as well as (±)-convolutamydines A and E, was achieved by transformation of the allyl moiety of 3-allyl-3-hydroxyindolin-2-ones.