Monooxygen donation potential of 4a-hydroperoxyflavins as compared with those of a percarboxylic acid and other hydroperoxides. Monooxygen donation to olefin, tertiary amine, alkyl sulfide, and iodide ion
Oxidative Addition of Halogens on Open Metal Sites in a Microporous Spin-Crossover Coordination Polymer
作者:Gloria Agustí、Ryo Ohtani、Ko Yoneda、Ana B. Gaspar、Masaaki Ohba、Juan F. Sánchez-Royo、M. Carmen Muñoz、Susumu Kitagawa、José A. Real
DOI:10.1002/anie.200904379
日期:2009.11.9
porous spin‐crossover framework Fe(pz)[PtII(CN)4]} to X2 (pz=pyrazine; X2=Cl2, Br2, and I2) leads to incorporation of the halides in the coordinatively unsaturated [PtII(CN)4]2− moieties through oxidativeaddition, thus affording the mixed‐valence series Fe(pz)[PtII/IV(CN)4(X)]}, which features quite distinct cooperative spin‐transition properties.
与客人混合:多孔自旋交联骨架Fe(pz)[Pt II(CN)4 ]}暴露于X 2(pz =吡嗪; X 2 = Cl 2,Br 2和I 2)通过氧化加成将卤化物掺入配位不饱和的[Pt II(CN)4 ] 2-部分中,从而提供了混合价系列Fe(pz)[Pt II / IV(CN)4(X)]},它具有非常独特的协同自旋转变性质。
One- Versus Two-Electron Oxidation with Peroxomonosulfate Ion: Reactions with Iron(II), Vanadium(IV), Halide Ions, and Photoreaction with Cerium(III)
The kinetics of the redox reactions of the peroxomonosulfate ion (HSO5−) with iron(II), vanadium(IV), cerium(III), chloride, bromide, and iodide ions were studied. Cerium(III) is only oxidized upon illumination by UV light and cerium(IV) is produced in a photoreaction with a quantum yield of 0.33 ± 0.03. Iron(II) and vanadium(IV) are most probably oxidized through one-electron transfer producing sulfate
A Thioether-Ligated Cupric Superoxide Model with Hydrogen Atom Abstraction Reactivity
作者:Mayukh Bhadra、Wesley J. Transue、Hyeongtaek Lim、Ryan E. Cowley、Jung Yoon C. Lee、Maxime A. Siegler、Patrick Josephs、Gerald Henkel、Markus Lerch、Siegfried Schindler、Adam Neuba、Keith O. Hodgson、Britt Hedman、Edward I. Solomon、Kenneth D. Karlin
DOI:10.1021/jacs.1c00260
日期:2021.3.17
([1]+), and its O2-bound analog [(TMGN3S)CuII(O2•–)]+ ([1·O2]+). The latter is the first reported cupric superoxide with an experimentally proven Cu–S bond which also possesses demonstrated hydrogenatomabstraction (HAA) reactivity. Introduction of O2 to a precooled solution of the cuprous precursor [1]B(C6F5)4 (−135 °C, 2-methyltetrahydrofuran (2-MeTHF)) reversibly forms [1·O2]B(C6F5)4 (UV/vis spectroscopy:
通过非偶联双核铜单加氧酶(如多巴胺-β-单加氧酶)在激素和神经递质生物合成中提出的超氧化铜中间体的核心作用引起了人们对此类铜M(“Cu B ”)活性位点的不寻常蛋氨酸连接的极大关注。酶。铜-硫的相互作用已被证明对营业额至关重要,这引发了关于 Nature 选择可氧化的 Met 残基以促进 C-H 氧化的仍未解决的问题。我们在此描述了 Cu M、[( TMG N 3 S)Cu I ] + ([ 1 ] + ) 及其 O 2的模型结合类似物[( TMG N 3 S)Cu II (O 2 •– )] + ([ 1 ·O 2 ] + )。后者是第一个报道的具有实验证明的 Cu-S 键的超氧化铜,该键还具有证明的氢原子夺取 (HAA) 反应性。将 O 2引入亚铜前体 [ 1 ]B(C 6 F 5 ) 4 (-135 °C, 2-甲基四氢呋喃 (2-MeTHF))的预冷溶液中可逆地形成 [ 1 ·O 2
Syntheses, crystal structures, reactivity, and photochemistry of gold(iii) bromides bearing N-heterocyclic carbenes
作者:Christa Hirtenlehner、Charlotte Krims、Johanna Hölbling、Manuela List、Manfred Zabel、Michel Fleck、Raphael J. F. Berger、Wolfgang Schoefberger、Uwe Monkowius
DOI:10.1039/c1dt11175b
日期:——
Gold(I) complexes bearing N-heterocyclic carbenes (NHC) of the type (NHC)AuBr (3a/3b) [NHC = 1-methyl-3-benzylimidazol-2-ylidene (= MeBnIm), and 1,3-dibenzylimidazol-2-ylidene (= Bn2Im)] are prepared by transmetallation reactions of (tht)AuBr (tht = tetrahydrothiophene) and (NHC)AgBr (2a/2b). The homoleptic, ionic complexes [(NHC)2Au]Br (6a/6b) are synthesized by the reaction with free carbene. Successive oxidation of 3a/3b and 6a/6b with bromine gave the respective (NHC)AuBr3 (4a/4b) and [(NHC)2AuBr2]Br (7a/7b) in good overall yields as yellow powders. All complexes were characterized by NMR spectroscopy, mass spectrometry, elemental analysis and single crystal X-ray diffraction. Reactions of the Au(III) complexes towards anionic ligands like carboxylates, phenolates and thiophenolates were investigated and result in a complete or partial reduction to a Au(I) complex. Irradiation of the Au(III) complexes with UV light yield the Au(I) congeners in a clean photo-reaction.
Isotope effects in the acid-catalysed reactions of hypophosphorous acid
作者:John W. Larson
DOI:10.1016/s0277-5387(00)81296-6
日期:1990.1
constants for four isotope exchange reactions and four oxidation reactions were measured at 25°C for protonated and deuterated hypophosphorous acid. For the acid-catalysed, rate-determining tautomerization of inactive H2PO(OH) to active HP(OH)2, primary kinetic isotopeeffects (kD/kH) of 0.36 for the forward reaction and 0.24 for the reverse reaction were obtained. The secondary isotope effect was determined