The Influence of HCl Concentration on the Rate of the Hydrolysis-Condensation Reaction of Phenyltrichlorosilane and the Yield of (Tetrahydroxy)(Tetraphenyl)Cyclotetrasiloxanes, Synthesis of All Its Geometrical Isomers and Thermal Self-Condensation of Them under "Pseudo"-Equilibrium Conditions.

The rate of hydrolysis-condensation reaction of phenyltrichlorosilane in water-acetone solutions and the product yields were shown to significantly depend on the concentration of HCl (C) in the solutions. The main product of the reaction was all-(tetrahydroxy)(tetraphenyl)cyclotetrasiloxane. This was different from the earlier published results of analogous reactions of -tolylSiCl, -ClPhSiCl, and -naphtylSiCl, in which some products of other types were formed.

A Study of the Influence of the HCl Concentration on the Composition and Structure of (Hydroxy)Arylsiloxanes from the Hydrolysis-Condensation Reaction of Aryltrichlorosilanes.

The hydrolysis-condensation reactions of -tolyl, -chlorophenyl, and -naphtyl-trichlorsilanes, (, , and , respectively) in water-acetone solutions were examined for how they were influenced by the change in the concentration of HCl (C). The composition of the products was monitored by Si NMR spectroscopy and atmospheric pressure chemical ionization mass spectrometry (APCI-MS). The acidity of the medium was shown to affect the yields of the products, and so, what products were formed.

Manganese(iii) acetate-mediated activation of C-H bonds of weak CH-acids; addition of o-carborane, its derivatives, and some other CH-acids to [60]-fullerene.

o-Carborane, 9-I-o-carborane, 1-Me-o-carborane, and several other CH-acids, 9H-fluorene, 2-Br-9H-fluorene, and trimethylsylylacetylene, have been shown to react with C60 affording their monoadducts with fullerene, the reaction being mediated by Mn(OAc)3·2H2O. In the case of o-carborane, when the molar ratio of C60 : o-carborane : Mn(OAc)3·2H2O was 1 : 21 : 20, polyaddition occurred to furnish adducts bearing between one and six o-C2HB10H10 groups. A distinguishing characteristic of the carboranyl derivatives of C60 obtained appeared to be that the carboranyl moieties were connected to the fullerenyl one by their carbon atom.

A mechanistic study of manganese(iii) acetate-mediated phosphonyl group additions to [60]- and [70]-fullerenes: the oxidative-ion-transfer mechanism vs. free radical addition.

The phosphonylation of C with HP(O)(OAlk) and Mn(OAc)·2HO has been considered to occur via a free radical (FR) path involving intermediate radicals ˙P(O)(OAlk). The present study provides evidence in support of another mechanism for the reactions, oxidative-ion-transfer (OIT). The mechanism involves the change of an acetate group in Mn(OAc) for the phosphonate group and oxidation of C by the Mn(OAc)P(O)(OAlk) formed to a pair: (C˙, Mn(OAc)P(O)(OAlk)˙) followed by the transfer of the phosphonate anion to give the monophposphonylfullerenyl radical.

Homolytic reactive mass spectrometry of fullerenes: peculiarities of the reactions of C60 with aromatic compounds in the ionization chambers of mass spectrometers and in solution.

C60 reacted with PhH, PhCl, BnH, BnNH2, and o-C2H2B10H10 in the electron impact (EI) ion source of a mass spectrometer at 300 °C forming phenyl, benzyl, and o-carboranyl adducts, respectively, stabilized by hydrogen addition and loss. Besides, the additions to C60 of methyl and phenyl radicals for toluene, and a phenyl radical for benzylamine were observed. A homolytic reaction mechanism was suggested involving the reaction of the radicals formed from the aromatics under EI with C60 at the ionization chamber walls.

Homolytic reactive mass spectrometry of fullerenes: interaction of C60 and C70 with ketones in the electron impact ion source of a mass spectrometer and the comparison of results with those of photochemical reactions of C60 with several ketones in solution.

Our previous investigations showed that homolytic reactions of C(60) with a number of perfluoroorganic and organomercury(II) compounds occurring under electron impact (EI) in the ionization chamber (IC) of a mass spectrometer could predict the reactivity of C(60) towards these compounds in solution or solid state. To expand the scope of this statement, C(60) and C(70) have been reacted with ketones RCOR(1), where R and R(1) are alkyl, aryl, benzyl, and CF(3), in an IC under EI to yield products of the addition of R(·) and R(1)(·) radicals to the fullerenes, paramagnetic ones being stabilized by hydrogen addition and loss. Experimental evidence in support of a mechanism involving homolytic dissociation of ketone molecules via superexcited states to afford these radicals that react with the fullerenes at the IC surface has been obtained.

Homolytic reactive mass spectrometry of fullerenes: interaction of C60 and C70 with organo- and organoelement mercurials in the electron impact ion source of a mass spectrometer; EPR, CIDEP, and MS studies of several analogous reactions of C60 performed in solution.

Interaction of C(60) with organo- and organoelement mercurials (CF(3)HgBr, PhHgBr, p-CH(3)C(6)H(4)HgBr, p-CH(3)OC(6)H(4)HgCl, CF(3)HgPh, Ph(2)Hg, (o-carborane-9-yl)(2)Hg, (m-carborane-9-yl)(2)Hg, (p-carborane-9-yl)(2)Hg, and (m-carborane-9-yl)HgCl) in the ionization chamber (IC) of the electron impact (EI) ion source of a mass spectrometer at 250-300 degrees C results in the transfer of the corresponding organic or organoelement radicals from the mercurials to the fullerene. Some of the processes are accompanied by hydrogen addition. C(70) reacts with Ph(2)Hg and (o-carborane-9-yl)(2)Hg at 300 degrees C in a similar fashion.

Unusual addition patterns in trifluoromethylation of [60]fullerene.

From pyrolytic trifluoromethylation of [60]fullerene with CF3CO2Ag at 300 degrees C we have isolated ca. sixty C60(CF3)n isomers (numbers in parentheses) as follows: n = 2(1), 4(8), 6(13), 8(21), 10(11), 12(5), 14(4), twenty-one of which have been characterised by 19F NMR. Compounds with addition levels up to n = 20 have also been identified.