Yu. I. Lyakhovetskii

Radical functionalization of [60]fullerene and its derivatives initiated by the C(CF3)2C6H4F radical

It was found that the 2-(p-fluorophenyl)hexafluoroisopropyl radical produced by thermal dissociation of the Polishchuk dimer [C(CF3)2C6H4F]2 can withdraw, under mild conditions, the H atom from the methyl group of toluene and mesitylene to form the corresponding radicals, whose addition to [60]fullerene occurs more selectively than in the case of photochemical production of these radicals. Dynamics of the step-by-step multiaddition of the radicals to C60 was studied by ESR. It was found that the addition of benzyl radicals affords adducts containing from 3 to 5 benzyl groups, whereas no spin-adducts with five addends were observed for more bulky 3,5-dimethylphenylmethyl radicals. The interaction of 3,5-dimethylphenylmethyl radicals with the metal complexes (η2-C60[IrH(CO)(PPh3)2] and (η2-C60[Pd(PPh3)2] was studied for the first time. It was shown that the palladium derivative undergoes only demetallation. In the case of the Ir complex, up to 3 radicals add to the fullerene ligand in the same hemisphere where the transition metal is coordinated. The reaction rates are ∼5 times lower than those for C60. The ability of 2-(p-fluorophenyl)hexafluoroisopropyl radicals to dehydrogenate C60H36 was found.

Influence of added salts and acids on the ionic hydrogenation of thiophenes

1. The ionic hydrogenation of thiophenes is greatly accelerated by a large excess of trifluoroacetic acid or small quantities of p-toluenesulfonic acid or neutral salts (lithium perchlorate and lithium tosylate). 2. In the hydrogenation of 2-ethylthiophene use of excess CF3COOH or addition of p-toluenesulfonic acid or LiClO4 not only accelerates the reaction but also increases the yield of 2-ethyltetrahydrothiophene.

Preparation of 2,2′-octahydrodithienyl and its complexes with HgCl2 and CdCl2

The ionic hydrogenation of 2,2′-dithienyl with triethylsilane and trifluoroacetic acid gave 2,2′-octahydrodithienyl, which was characterized by its complexes with HgCl2 (II) and CdCl2 (II).

Synthesis of branched deuterohydrocarbons, containing deuterium at a tertiary carbon atom

A method for the synthesis of branched deuterohydrocarbons, containing duterium attached to a tertiary carbon atom, was proposed on the basis of the ionic hydrogenation reaction.

One-electron transitions in the systems dipotassium salt of the cyclooctatetraene dianion-benz-X-diazoles (X=Se, S)

1. In the interaction of dipotassium salt of the cyclooctatetraene dianion with benz-[1,2-c]-[1,2-5]-X-diazoles (X=Se, S) in tetrahydrofuran, there is an electron transfer with the formation of cyclooctatetraene and the corresponding potassium salts of benzdiazole anion radicals. 2. In the case of benz-[1,2-c]-[1,2,5]-thiadiazole, the yield of cyclooctatetraene does not exceed 15%, and an equilibrium is established among all four components of the reaction. For the β-chloroderivative, the equilibrium is substantially shifted in the direction of formation of cyclooctatetraene; the introduction of a methyl group or methoxy group into theβ-position of piazthiol does not have any effect. 3. In the interaction of the cyclooctatetraene dianion with benz-[1,2,-c]-[1,2,5]-selenadiazole, cyclo-octatetraene is formed in quantitative yield, while in the interaction withβ-methyl- orβ-methoxysubsti-tuted benzselenadiazoles, it is formed in a yield of up to 90%. 4. It is proposed that the state of equilibrium of the reaction of the dipotassium salt of the cyclo-octatetraene dianion with the investigated electron acceptors in tetrahydrofuran is due to the fact that the corresponding potentials of one-electron reduction are brought closer together on account of the formation of ion pairs including the potassium cation.

One-electron transfer in the reactions of polyfluoroketones with organic donors

Phenol derivatives and sodium phenolates react with hexafluoroacetophenone (1) and its analogs (2) and (3) to form only the C-oxyalkylation products in high yield [ 1]. In some cases, a dark violet color is noted for the reaction mixture, which disappears upon completion of the reaction, indicating the possible participation of intermediates. Attempts to detect radical species in the reaction medium using ESR spectroscopy were unsuccessful. However, a strong signal for aroxyl radical (A) was detected in the ESR spectra in a model reaction of polyfluorocarbonyl compounds 1-3 with sodium 2,4,6-tris-tert-butylphenolate, i.e., compounds, in which substitution reactions are impossible.

Main products and nature of the decomposition of ?-allyl-carbonyl complexes of iron

The decomposition of C3H5Fe(CO)3X, where X=I, NO3, under various conditions has been studied. Its decomposition has given products of the doubling of the allyl radical and iron carbonyl and, in polar media, propylene as well. Under certain conditions, carbonylation of the allyl residue takes place.