Palladium and platinum catalyzed hydroselenation of alkynes: SeH vs SeSe addition to CC bond

A mechanistic study of the hydroselenation of alkynes catalyzed by Pd(PPh₃)₄ and Pt(PPh₃)₄ has shown that the palladium complex gives products of both SeH and SeSe bond addition to the triple bond of alkynes, while the platinum complex selectively catalyzes SeH bond addition. The key intermediate of PhSeH addition to the metal center, namely Pt(H)(SePh)(PPh₃)₂, was detected by ¹H-NMR spectroscopy. The analogous palladium complex rapidly decomposes with evolution of molecular hydrogen. A convenient method was developed for the preparation of Markovnikov hydroselenation products H₂CC(SePh)R, and the scope of this reaction was investigated. The first X-ray structure of the Markovnikov product H₂CC(SePh)CH₂N⁺HMe₂·HOOCCOO⁻ is reported.     

Reaction of CBrF2-CBrF2 with hydrazones of aromatic aldehydes: Novel efficient synthesis of fluorocontaining alkanes, alkenes and alkynes

An olefination of hydrazones of aromatic aldehydes by CBrF₂-CBrF₂ under copper catalysis was investigated. In situ prepared aldehydes hydrazones were converted to (3-bromo-2,2,3,3-tetrafluoropropyl)arenes by reaction with CBrF₂-CBrF₂ in the presence of CuCl. Subsequent elimination of HF by sodium hydroxide resulted in stereospecific formation of fluorocontaining alkenes. Elimination proceeds stereoselectively, only Z-isomers of alkenes are formed. Elimination of two molecules of HF from (3-bromo-2,2,3,3-tetrafluoropropyl)arenes by treatment with potassium tert-butoxide leads to formation of (bromodifluoromethyl)alkynes. As a result a simple and efficient transformation of aromatic aldehydes to range of various fluorinated alkanes, alkenes and alkynes was elaborated.     

PHOTOBIOLOGY OF RNA BACTERIOPHAGES—I. ULTRAVIOLET INACTIVATION AND PHOTOREACTIVATION STUDIES*

Abstract— Biologically active f2-RNA, Obtained from bacteriophage f2, was inactivated by ultraviolet (u.v) light (2537 Å) with a quantum yield of 3.3 ± 0.3 times 10^-3 when assayed in the dark with protoplasts of an F- strain of E. coli k12. Assay under “black light” gave a quantum yield of 2.7 ± 0.5 times 10^-3 which was just enough lower to suggest that 17 per cent photorecovery of the u.v. lesions has taken place. Intact phage f2 was inactivated by u.v. radiation with a quantum yield of 0.7 ± 0.12 times 10^-3, Thus the whole phage is much less sensitive than the free RNA. No evidence of photorecovery was found in u.v.-irradiated RNA phage 7S assayed in its host Pseudomonas aeruginosa.     

A new protocol for a regioselective aldol condensation as an alternative convenient synthesis of beta-ketols and alpha,beta-unsaturated ketones

A general and convenient synthesis of beta-ketols and alpha,beta-alkenones has been achieved by a Knoevenagel condensation of a beta-ketoacid with an aldehyde in aqueous medium. Saponification of a beta-ketoester by an aqueous KOH 10% solution gives the potassium salt of the beta-ketoacid, which is condensed in situ with an aldehyde at pH 7.8-8.0, at 60 degrees C for 5-6 h. The intermediate beta-ketocarboxylate is smoothly decarboxylated in the reaction medium, giving the beta-ketol in high yield (75-90%). Acidification of the reaction mixture at pH 1 and heating at 70 degrees C under vigorous stirring for 6 h, leads directly to the corresponding alpha,beta-unsaturated ketone in good yield (65-75%).     

Eine Petroleumlampe zum Anheizen von Muffel?fen

Ohne Zusammenfassung     

Is it common for charge recombination to be faster than charge separation?

Attaining long-lived charge-transfer (CT) states is of the utmost importance for energy science, photocatalysis, and materials engineering. When charge separation (CS) is slower than consequent charge recombination (CR), formation of a CT state is not apparent, yet the CT process provides parallel pathways for deactivation of electronically excited systems. The nuclear, or Franck-Condon (FC), contributions to the CT kinetics, as implemented by various formalisms based on the Marcus transition-state theory, provide an excellent platform for designing systems that produce long-lived CT states. Such approaches, however, tend to underestimate the complexity of alternative parameters that govern CT kinetics. Here we show a comparative analysis of two systems that have quite similar FC CT characteristics but manifest distinctly different CT kinetics. A decrease in the donor-acceptor electronic coupling during the charge-separation step provides an alternative route for slowing down undesired charge recombination. These examples suggest that, while infrequently reported and discussed, cases where CR is faster than CS are not necessarily rare occurrences.     

Electrochemical analysis in charge-transfer science: The devil in the details

It is easy to carry out electrochemical analysis. It is demanding, however, to do it right, as inherent challenges, emerging from details in the data collection and the result interpretation, frequently present themselves. In pertinence to electron–donor–acceptor interactions, herein, we focus on voltammetrically obtained electrochemical potentials and their immense utility for extracting important characteristics of molecular analytes. Recommendations how to address key pending challenges, based on recent developments in electroanalysis and charge-transfer science, accompany the discussions on undesired impacts from irreversibility of oxidation and reduction, supporting electrolytes, choices of reference, liquid junctions, and ‘nonideality’ of molecular shapes. As the wide implications of charge transfer are indisputable, using the tools at our disposal for improving the reliability of electroanalysis is crucial for advancing modern science and engineering.