O. Yu. Okhlobystin

Acidity of the C-H bonds of derivatives of ortho- and metacarboranes

The capacity of several ortho- and metacarboranyl derivatives of mercury for polarographic reduction was investigated. The relative stability of the corresponding carbanions was presented.

Synthesis of hydrocarbon derivatives of barene

1. A number of hydrocarbons [derivatives] of the barene series were synthesized by the reaction of diacetonitriledecaborane with the appropriate acetylenic hydrocarbons. 2. The high thermal, hydrolytic, and oxidative stability of compounds of the barene series was demonstrated.

Synthesis of organometallic compounds from trialkylaluminums and metal salts

Reaction between trialkylaluminums and salts of antimony, bismuth, mercury, thallium, tin, and lead gives alkyl derivatives of these metals.

Some transformations of the anion radical of phenylbarene

1. The anion radical of phenylbarene with excess potassium forms the phenyldicarbododecaborane (14) dianion. 2. In the hydrolysis of the phenylbarene anion radical and the phenyldicarbodocecaborane dianion, the phenyldicarbododecaborane (14) anion is formed. 3. The oxidation of the phenylbarene anion radical by mercuric chloride gives phenylbarene in 92% yield.

Synthesis of heteroorganic derivatives of barene

It was shown by the example of phenylbarenyllithium and heteroorganic halides of silicon, tin, mercury, and phosphorus that lithium derivatives of barene can be successfully used to obtain heteroorganic compounds of a new class, where the heteroatom is directly bonded to the barene ring.

Use of organomagnesium compounds for the synthesis of organic derivatives of group II–V elements in a nonethereal medium

For the primary alkyl halides (R=from C2H5 to n-C9H19; halogen=C1, Br, and I) and the simplest aryl halides (R=C6H5 and p-CH3C6H4) it was shown that the organomagnesium synthesis in absence of catalysts for the Grignard reaction can be applied with success to the preparation of heteroorganic compounds of elements of Groups II–IV (mercury, boron, aluminum, silicon, germanium, tin, phosphorus, arsenic, antimony).

Chemical transformations of Β-chlorovinylmercury chlorides

1. It was shown that the stereoisomeric trans- and cis-Β-chlorovinylmercury chlorides undergo mutual transformation when either of the stereoisomers is heated above the melting point. A similar reversible isomerization also proceeds in the presence of mercuric chloride. 2. Treatment of the cis-isomer with sodium iodide and phenylmagnesium chloride leads, respectively, to the formation of symmetrization and substitution products, whereas the trans-isomer eliminates acetylene in both reactions.

Reaction of onium salts with nucleophilic reagents

1. The reaction of iodonium and diazonium salts with tertiary amines includes the step of a one-electron transfer from the amine molecule to the onium compound. 2. The reaction of iodonium and diazonium salts with alcoholates also proceeds as a reaction of a one-electron transfer.

Role of anion radicals in the synthesis of organometallic compounds

1. The formation of theα- andβ-fluoronaphthalene anion radicals was demonstrated by reacting the fluoronaphthalenes with alkali metals and by electrochemical reduction. 2. Data are presented showing that anion radicals are formed during the synthesis of organometallic compounds from halogenides and free metals.

Nuclear quadrupole resonance of Cl35, Br79, Br81, and I127 of halogen-containing organomercury compounds

1. The NQR spectra of halogens in a number of organomercury compounds of the RHgHal and p-ClC6 H4HgX types were investigated. 2. In crystals of the compounds studied, coordination interactions arise between the mercury atoms and the halogens. However, when the type of coordination is preserved within a narrow series of compounds, the changes in the NQR frequencies may be determined by the chemical nature of the substituents. 3. The chemical behavior of the HgHal group depends substantially on the degree of coordination saturation of the mercury atom.