Benzophenone vs. Copper/Benzophenone in Light‐Promoted Atom Transfer Radical Additions (ATRAs): Highly Effective Iodoperfluoroalkylation of Alkenes/Alkynes and Mechanistic Studies

Iodoperfluooralkylation of terminal alkenes and alkynes is effectively photo‐promoted by benzophenone 2 (BP) or the photoreducible copper(II) complex 1 . In particular, BP at 1 mol% in methanol upon 365 nm irradiation with a low‐pressure mercury lamp (type TLC=thin layer chromatography, 6 W) results in a fast reaction with excellent reaction yields. Complex 1 and BP 2 exhibited very similar reactivity, suggesting that the reactions involving 1 are likely to be governed by the benzophenone photoactivation processes, rather than copper(I)/(II) redox processes. Mechanistic investigations using transient absorption spectroscopy revealed that a deactivation pathway of the benzophenone triplet (³BP*) is via its reaction with the methanol solvent. We propose that the generated radicals, in particular ^.CH₂OH, play a key role in the initiation step forming R_f^. by reacting with R_fI, R_f^. then entering a radical chain cycle. ¹H NMR studies provided evidence that a substantial amount (∼7% NMR yield) of the hemiacetal CH₃OCH₂OH is formed, i.e., the possible by‐product of the reaction between ^.CH₂OH and R_fI. Finally, DFT calculations indicate that a triplet‐triplet energy transfer (TTET) process from ³BP* to perfluorooctyl iodide (C₈F₁₇I) is unlikely or should be rather slow under the reaction conditions, consistent with the transient absorption studies.

     

Exploring the Biosynthesized Metal Nanoparticles for their Catalytic Degradation of Toxic Water Wastes and Antimicrobial Potential

Journal of Inorganic and Organometallic Polymers and Materials - In recent decades, the analysis of nanoparticles is of greater importance for their applications in various fields. This present...     

Dynamic Effect of Soil-Tunnel Interface Under Dynamic Loading

Soil Mechanics and Foundation Engineering - The resilience of the Daikai subway station during the Kobe earthquake is taken as a case study of tunnel endurance at various points under different...     

About the Nature of Quasi-Cleavage in Low-Carbon Steel Embrittled with Hydrogen

Metal Science and Heat Treatment - Scanning electron microscopy and confocal laser scanning microscopy are used to study a fracture surface of hydrogen-charged low-carbon steel, which has been...     

Experimental Search for Chemical Compositions of Superelastic Titanium Alloys with Enhanced Functional Properties

Metal Science and Heat Treatment - Ti – Zr-based alloys with a high zirconium content prepared by vacuum-arc remelting with nonconsumable tungsten electrode are studied. The optimum number of...     

Polymerization of propylene in liquid monomer using state-of-the-art high-performance titanium-magnesium catalysts

A comparative study of propylene polymerization in liquid monomer is performed under laboratory conditions using the IK-8-21 Ti-Mg catalyst designed at the Boreskov Institute of Catalysis and imported industrial catalysts (conditionally labeled TMC-1, -2, and -3). The activity and stereospecificity of the catalysts are estimated along with properties of the resulting polypropylene (granular composition and physicomechanical characteristics). It is shown that the IK-8-21 catalyst is not inferior to imported counterparts in terms of catalytic properties in the synthesis of polypropylene. The polypropylene powder formed on IK-8-21 is homogeneous and has good morphology. The physicomechanical characteristics of polypropylene synthesized on the domestic IK-8-21 catalyst are similar to those for polypropylene prepared with the imported TMK-1 catalyst.     

Feasibility of Using Titanium Machine Turnings in Powder Metallurgy Processes

JOM - The use of titanium machine turnings has been identified as a possible ultralow-cost method to produce titanium powder. However, very little data are available on the viability of this...     

Absolute Isotherms of Adsorption of Components of Binary Liquid Solutions of Macro- and Microporous Adsorbents

Protection of Metals and Physical Chemistry of Surfaces - The methods of describing absolute adsorption isotherms of binary nonelectrolyte solutions components on macro- and microporous adsorbents...     

Pitting Corrosion of Carbon Steel in Chloride-Containing Saturated Ca(OH)2 Solutions

Protection of Metals and Physical Chemistry of Surfaces - Pitting formation in carbon steel in saturated Ca(OH)2 solutions containing different concentrations of added NaCl is studied...     

Cleaning of Humidified Gas Media from Benzene Using Active Carbons Modified by Fullerenes

Protection of Metals and Physical Chemistry of Surfaces - Comparison of methods for modification of active carbon by fullerenes with and without a stabilizer is presented. The possibility of...