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.     

Synthesis,structure, and properties of 2-[(4,6-di-tert-butyl-2,3-dihydroxyphenyl)thio]acetic acid amides

Russian Chemical Bulletin - New potential biologically active derivatives, in which the sterically hindered pyrocatechol moiety is linked through a 2-thioacetyl covalent bridge to a number of...     

Synthesis of functionalized tetrahydropyridones by the tandem Knoevenagel—Michael—intramolecular ammonolysis—alkylation reaction

Russian Chemical Bulletin - The tandem Knoevenagel—Michael—intramolecular ammonolysis—alkylation reaction was used to synthesize functionalized tetrahydropyridones. The molecular...     

Kinetic regularities of thermal decomposition of polycarbonate films containing Pt,Au, Ag,and Ni nanoparticles

Russian Chemical Bulletin - The kinetic regularities of thermal destruction of polycarbonate films containing Pt, Au, Ag, and Ni nanoparticles were studied. Scanning and transmission electron...     

Determination of Indicator Congeners of Polychlorinated Biphenyls in Water at Ultratrace Levels by Gas Chromatography–Tandem Mass Spectrometry

Journal of Analytical Chemistry - We validated a procedure for the determination of indicator congeners (ICs) of polychlorinated biphenyls (PCBs) (IUPAC nos. 28, 52, 101, 118, 138, 153, and 180) in...     

Stability of Highly Concentrated Water-in-Oil Emulsions with Magnetic Nanoparticles and the Structure of Highly Porous Polymers Formed on Their Basis

Colloid Journal - The influence of the concentration and size of magnetite nanoparticles on the stability of highly concentrated water-in-oil emulsions containing styrene–divinylbenzene...     

Synthesis and evaluation of the antioxidant properties for some novel aminomethyl derivatives of 2,6-diisobornylphenol bearing a pinane moiety

Some new derivatives based on 2,6-diisobornylphenol and containing amine moieties of the pinane structure at the para-position relative to the phenolic hydroxy group were synthesized. The antioxidant properties of the obtained compounds were estimated using various in vitro models. The introduction of diamine moiety into a starting molecule led to a significant increase in the radical scavenging activity and the ability to chelate Fe²⁺ ions.

     

Effect of MQ-copolymer and polymethylsilsesquioxane on thermal and mechanical properties of highly filled polyisoprene

Russian Chemical Bulletin - Highly filled vulcanizates based on polyisoprene, organosilicon fillers (polymethylsilsesquioxane and MQ-copolymers), and p-quinone dioxime derivative as a rubber...     

An Approach to Structural and Functional Modeling of the Surface Morphology of Materials Based on Fluorinated Polymers

Russian Journal of General Chemistry - Dynamic modeling of the polymodal morphological structure of the polymer surface, with modified polyethylene terephthalate as an example, was performed. In...     

Syntheses,Structural Characterization of Two Cobalt Coordination Polymers Composed of Isophthalate and Bis(4-(1H-imidazol-1-YL)phenyl)methanone Ligands

Russian Journal of Coordination Chemistry - Two 2D cobalt complexes, namely {[(Bipmo)2Co2(Ipa)2](DMF)]·2.25H2O}n (I), {[(Bipmo)-Co(Ipa)]·2H2O}n (II), have been constructed solvothermally...