Polyol-Metall-Komplexe. 25. rac-Mannose,rac-Arabit und L-Threit als deprotonierte Liganden in Ferraten(III)

Polyol Metal Complexes. 25. rac-Mannose, rac-Arabitol and L -Threitol as Deprotonated Ligands in Ferrates(III ) Ba₂[Fe₂(β-rac-ManfH_?5)₂] · 12H₂O ( 1 ), Sr₄[Fe₄(rac-Arab1,2,3,5H_?4)₄(OH)₂]CO₃ · 33 H₂O ( 2 ), and Ba₂[Fe₂(L-ThreH_?4)₂(OH)₂] · 12.5 H₂O ( 3 ) (Man = mannose, Arab = arabitol, Thre = threitol) have been crystallized from alkaline aqueous solution. Crystal structure analysis revealed dinuclear ferrate(III ) ions for 1 and 3 , the former being a C_i-symmetrical homoleptic ferric complex with pentadentate pentaanions derived from racemic β-mannofuranose. In 3 , besides tetradentate L -threitolato ligands, there is one terminal hydroxo ligand at each ferric center. Hydroxo ligands are also present in the C_i-symmetrical hexaanions of 2 , which are tetranuclear planar entities built up from four edge-sharing FeO₆ octahedra. However arabitol is a pentitol, the tetraanionic ligands are only tetradentate for steric reasons.     

Lateral Metallation and Redistribution Reactions of Sodium Ferrates Containing Bulky 2,6-Diisopropyl-N-(trimethylsilyl)anilide Ligands

Alkali-metal ferrates containing amide groups have emerged as regioselective bases capable of promoting Fe−H exchanges of aromatic substrates. Advancing this area of heterobimetallic chemistry, a new series of sodium ferrates is introduced incorporating the bulky arylsilyl amido ligand N(SiMe₃)(Dipp) (Dipp=2,6-iPr₂-C₆H₃). Influenced by the large steric demands imposed by this amide, transamination of [NaFe(HMDS)₃] (HMDS=N(SiMe₃)₂) with an excess of HN(SiMe₃)(Dipp) led to the isolation of heteroleptic [Na(HMDS)₂Fe{N(SiMe₃)Dipp}]_∞ ( 1 ) resulting from the exchange of just one HMDS group. An alternative co-complexation approach, combining the homometallic metal amides [NaN(SiMe₃)Dipp] and [Fe{N(SiMe₃)Dipp}₂] induces lateral metallation of one Me arm from the SiMe₃ group in the iron amide furnishing tetrameric [NaFe{N(SiCH₂Me₂)Dipp}{N(SiMe₃)Dipp}]₄ ( 2 ). Reactivity studies support that this deprotonation is driven by the steric incompatibility of the single metal amides rather than the basic capability of the sodium reagent. Displaying synergistic reactivity, heteroleptic sodium ferrate 1 can selectively promote ferration of pentafluorobenzene using one of its HMDS arms to give heterotrileptic [Na{N(SiMe₃)Dipp}(HMDS)Fe(C₆F₅)]_∞ ( 4 ). Attempts to deprotonate less activated pyridine led to the isolation of NaHMDS and heteroleptic Fe(II) amide [(py)Fe{N(SiMe₃)Dipp}(HMDS)] ( 5 ), resulting from an alternative redistribution process which is favoured by the Lewis donor ability of this substrate.     

The Electronic Ground State of [Fe(CO)3(NO)]−: A Spectroscopic and Theoretical Study

During the past 10 years iron‐catalyzed reactions have become established in the field of organic synthesis. For example, the complex anion [Fe(CO)₃(NO)]^?, which was originally described by Hogsed and Hieber, shows catalytic activity in various organic reactions. This anion is commonly regarded as being isoelectronic with [Fe(CO)₄]^2?, which, however, shows poor catalytic activity. The spectroscopic and quantum chemical investigations presented herein reveal that the complex ferrate [Fe(CO)₃(NO)]^? cannot be regarded as a Fe^?II species, but rather is predominantly a Fe⁰ species, in which the metal is covalently bonded to NO^? by two π‐bonds. A metal–N σ‐bond is not observed.     

高铁酸盐稳定性研究进展

高铁酸盐具有强氧化性和无毒性,是一种多用途化学试剂,可作为氧化剂、混凝剂、消毒剂和电池阴极材料使用.但高铁酸盐水溶液极易分解及固态高铁酸盐制备成本高,从而限制了它的实际应用.本文概述了高铁酸盐稳定性方面的研究进展,介绍了溶液浓度、pH、温度、高铁酸盐纯度和离子掺杂等因素对其稳定性的影响,以及改善高铁酸盐稳定性的各种研究...     

Cerium effect on the phase structure, phase stability and redox properties of Ce-doped strontium ferrates

Nanostructured perovskite-type Sr_1−aCe_aFeO_3−x, (0?a<0.15) powders have been prepared by citrate-nitrate smoldering auto-combustion. Their phase structure and stability, surface and morphological properties, reduction behavior and interaction with oxygen have been investigated by X-ray Powder Diffraction combined with Rietveld Analysis, ⁵⁷Fe Mössbauer and X-ray Photoelectron Spectroscopies, N₂-adsorption method, Temperature Programmed Reduction and Oxidation experiments. Our results reveal that citrate-nitrate auto-combustion method is effective in obtaining single phase Sr_1−aCe_aFeO_3−x. The Sr_1−aCe_aFeO_3−x structure is cubic only for a?0.06, while for a<0.06 remains tetragonal. Moreover, for a?0.06 after semi-reductive treatment under inert gas, an expanded cubic phase is obtained instead of the brownmillerite-type structure, which is known to have ordered vacancies. Stabilization of octahedral Fe³⁺ by cerium doping appears to be the main factor in determining the structural properties of Sr_1−aCe_aFeO_3−x. The highest oxygen consumption for Ce-doped SrFeO₃ occurs for a=0.06. Preliminary impedance measurements show that Sr_0.94Ce_0.06FeO_3−x has the lowest area-specific resistance.     

X-ray and Mössbauer study of structural changes in K3Na(FeO4)2

Mixed potassium–sodium ferrate(VI), K₃Na(FeO₄)₂, has been synthesized by precipitation from alkaline solution. At room temperature it decomposes spontaneously giving Fe(III) compounds and ferrate(VI) with a structure similar to that of K₂FeO₄, which is confirmed by X-ray diffraction and Mössbauer spectroscopy.     

高铁酸盐:一种绿色的多功能水处理剂

多种新型污染物和微生物污染等问题的出现,导致地表水水质复杂多变,传统的水处理药剂和处理方式已无法满足人们对饮用水处理的需求。 高铁酸盐作为一种新型水处理试剂,同时具备优良的氧化性和混凝性,而且不会引起二次污染,是一种可大力开发的绿色试剂。 本文综述了高铁酸盐净水剂的制备与表征分析方法,及其用于水处理对重金属、新型污染物和微生物等去除的作用机制。 目前,有关高铁酸盐用于有机污染物去除的混凝和氧化去除协同作用的研究尚不多见,高铁酸盐的氧化-混凝协同特性尚未被充分开发。 本文以此为重点进行了讨论,并对高铁酸盐净水剂的应用进行了展望。     

Structural and Synthetic Insights into Sodium-Mediated-Ferration of Fluoroarenes

Exploiting chemical cooperation between Na and Fe(II) within the bimetallic base [dioxane ⋅ NaFe(HMDS)₃] ( I ), (dioxane=1,4-dioxane, HMDS=N(SiMe₃)₂) the selective ferration of fluorobenzene, 1-fluoronaphthalene, 1,4-difluorobenzene, 1,2,4-trifluorobenzene, 1,3,5-trifluorobenzene, 1-bromo-3,5-difluorobenzene, 3-fluoroanisole and 3,5-difluoroanisole has been realized, affording sodium ferrates [dioxane ⋅ Na(HMDS)(2-F-C₆H₄)Fe(HMDS)]_∞ ( 1 ), [dioxane ⋅ Na(HMDS)(2-F-C₁₀H₆)Fe(HMDS)]_∞ ( 2 ), [dioxane ⋅ {Na(HMDS)(2,5-F₂-C₆H₃)Fe(HMDS)}₂]_∞ ( 3 ), [dioxane ⋅ {Na(HMDS)(2,3,6-F₃-C₆H₂)Fe(HMDS)}₂]_∞ ( 4 ), [(dioxane)_1.5 ⋅ Na(HMDS)(2,4,6-F₃-C₆H₂)Fe(HMDS)]₂ ( 5 ), [(dioxane)_1.5 ⋅ {Na(HMDS)(4-Br-2,6-F₂-C₆H₂)Fe(HMDS)₂] ( 6 ), [{(dioxane)₂ ⋅ Na₂Fe(HMDS)₂(2-methoxy-6-F-C₆H₃)}⁺{Fe(HMDS)₃}⁻]_∞ ( 7 ) and [dioxane ⋅ {Na(HMDS)(4-methoxy-2,6-F₂-C₆H₂)Fe(HMDS)}₂]_∞ ( 8 ), respectively. Reactions take place under mild reaction conditions, with excellent control of the selectivity and no competing C−F bond activation is observed. Showcasing complex polymeric arrangements in some cases, the structures of compounds 1 – 8 have been determined by X-ray crystallographic studies. In all cases, the Fe(II) centers occupy the position in the relevant fluoroarene that was previously filled by a proton, confirming that these metallations are actually ferration processes whereas the Na atoms prefer to form Na⋅⋅⋅F dative interactions. Compounds 1 – 8 are thermally stable and do not undergo benzyne formation (through NaF elimination) and their formation contrasts with the inertness of Fe(HMDS)₂ which fails to act as a base to metallate fluoroarenes.