A. Ya. Usyatinskii

Solid-state mechanochemical synthesis of cobalt(III), iron(III), and chromium(III) bisdicarbollyl complexes

Thallous dicarbollide reacts with cobalt(II), iron(III) and chromium(III) chlorides without a solvent under conditions of mechanical activation to form the corresponding carborane complexes of tervalent metals.

Carboranyl derivatives of group III non-transition metals

Only compounds of boron and thallium have been reported in the series of carboranyl derivatives of group III elements [1-3]. We are the first to report the preparation of oaluminum, gallium, and indium carboranes. The synthesis of C-carboranyl derivatives of AI m Ga, and In was carried out by two methods: I) carboranylation of compounds with a metal-halide bond using C-lithium carboranes and 2) metallation of carborane by alkyl derivatives of AI, Ga, and In in argon (method 2 was also used for thallium derivatives).

Cleavage of B-Ti bond in borothallated carboranes

Conclusions1.The B-Ti bond in borothallated carboranes is cleaved under photolysis and pyrolysis conditions.2.Some 9-thiocyanatocarboranes were synthesized.3.Alkyl-(B-carboranyl)thallium halides were obtained by the alkylation of carboranyl-thallium di(trifluoroacetates).

Reaction of carboranes with alkyl derivatives of group III metals

Conclusions1.Carboranyl derivatives of aluminum, gallium, and indium, containing a Ccarb-M bond, were obtained.2.Carboranes react with trimethylgallium etherate in the presence of tetramethyl-ethylenediamine to give gallium-containing dicarbaundecaborate ions.

Direct electrochemical synthesis of anionic complexes of thallium halides

ConclusionUsing a platinum cathode and thallium anode, electrolysis of solutions containing halogens results in the formation of anionic complexes of univalent and trivalent thallium depending on the nature of the halogen and electrolyte.

Structure of carboranyl derivatives of thallium(III)-crystal and molecular structure of (C,C′-dimethyl-m-carboran-9-yl)thallium chloride

Conclusions1.By means of IR and Raman spectroscopy, it has been shown that carboranyl derivatives of thallium of the type (C2H11B10)2TlX apparently consist of dimers with halogen bridge atoms.2.The crystal and molecular structure of (C, C′-dimethyl-m-carboran-9-yl)thallium dichloride has been determined. As a result of “weak” interactions Tl...Cl in the crystal, infinite chains are formed, the elementary units of which include a planar four-membered Tl2Cl2 ring.

Oxidation of carboranes by thallium(III) in the presence of palladium(II) as a new route to biscarboranes

ConclusionsBis(1,2-dimethyl-o-carborane) is formed when 1,2-dimethyl-o-carborane is oxidized by thallium(III) trifluoroacetate in the presence of 10% of Pd(II) acetate in CF3COOH solution.

Reaction of borothallated carboranes with zero-valent mercury and sulfur

Conclusions1.The B-T1 bond in borothallated carboranes is cleaved by Hg metal, which leads to carboranylmercury salts.2.The reduction of the reaction products of (B-carboranyl) thallium with elemental sulfur by LiAlH4, gave (B-carboranyl) mercaptans.

Thallium derivatives of p-carborane

Conclusions1.Some thallium derivatives of p-carborane, containing the carborane carbon-thallium and boron-thallium bonds, were synthesized.2.In their properties the T1 derivatives of p-carborane resemble the corresponding Tl derivatives of the o-and m-carboranes.

Characteristics of reductive cleavage of (B-Carboranyl)-thiocyanates

Conclusions1.(B-Carboranyl)thiocyanates are reduced by the dipotassium salt of cyclooctatetraene at the S-C bond.2.Borothallated carboranes are reduced by C8H8K2 at the B-T1 bond, in which connection the composition of the reaction products depends on the nature of the anion attached to the metal atom.