V. D. Makhaev

Solid-state mechanochemical synthesis of ferrocene

Abstract Solid-state mechanochemical reactions of iron(II) chloride with cyclopentadienides of alkaline metals or thallium, which lead to the formation of ferrocene, were studied. The dependence of the yield of the product on the parameters of mechanical loading for the reaction with cyclopentadienylthallium was determined.

Oxidation of 1-alkylcycloalkanols with PbIV and MnIII compounds under mechanical activation

A mechanoactivated solid-state oxidative decyclization of 1-alkylcycloalkanols under the action of the Pb(OAc)4−MX or Mn(OAc)3−MX systems (MX is a metal halide) was carried out for the first time. The reaction affords exclusively ω-haloalkanones.

X-RAY PHOTOELECTRON SPECTRA OF POLYHYDRIDO COMPLEXES OF TUNGSTEN AND MOLYBDENUM

Abstract X-Ray photoelectron spectroscopy has been applied to study MH4L4(M = or Mo, L = PHPh2, PMePh2, PEtPh2, PBuPh2, PEt2Ph, P(OPr-i)3 or 1 2 dppe). It has been shown that tungsten in these compounds has a negative charge whereas the charge of molybdenum is almost zero.

(S)-(−)-(2-MeBu)N(Pr)2MeI Salt as Template in the Enantioselective Synthesis of the Enantiopure Two-dimensional (S)-(−)-(2-MeBu)N(Pr)2Me[ΛMnΔCr(C2O4)3] Ferromagnet

We describe herein the synthesis of (rac)- or enantiopure (S)-(-)-(2-MeBu)N(Pr)₂MeI ammonium salts. These racemic and enantiopure ammonium salts were used as cationic templates to obtain new two-dimensional (2D) ferromagnets [(rac)-(2-MeBu)N(Pr)₂Me][MnCr(C₂O₄)₃] and [(S)-(-)-(2-MeBu)N(Pr)₂Me][ΔMnΛ nCr(C₂O₄)₃]. The absolute configuration of the hexacoordinated Cr(III) metallic ion in the enantiopure 2D network was determined by a circular dichroism measurement. The structure of [(2-MeBu)N(Pr)₂Me][MnCr(C₂O₄)₃], established by single crystal X-ray diffraction, belongs to the chiral P63 space group. According to direct current (dc) magnetic measurements, these compounds are ferrromagnets with a temperature Tc = 6°K.

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.

Polymerization of ethylene with the (C5H5)4Zr-methylaluminoxane soluble catalytic system

The effects of catalyst concentration, Al-to-Ti molar ratio, hydrogen additives, and time of aging of catalyst components on the kinetic features of ethylene polymerization in the presence of the (C5H5)4Zr-methylaluminoxane soluble catalytic system in toluene and hexane at 60°C and an ethylene pressure of 0.6 MPa have been studied. It has been demonstrated that the highest activity and productivity of the title system is achieved in the presence of 0.9% H2 in the gas phase of a reactor (2180 kg PE/(g Zr h)). When polymerization is carried out in hexane, the rate constant of chain propagation is lower by a factor of ∼1.5 than that in the case of toluene and the catalytic system is characterized by a long lifetime.

Oxidation of aliphatic alcohols with the lead tetraacetate—metal halide system under mechanical activation

The mechanochemical oxidation ofn-pentanol,n-hexanol, andn-octanol with the Pb(OAc)4-MHal system (M=Li, K; Hal=Cl, Br) in the absence of a solvent affords esters. and secondary alcohols with the composition C8H17OH and C9H19OH give ketones.

Production of manganese borohydride complexes of manganese solvated with THF, and the structure of Mn(BH4)2 (THF)3

ConclusionsBy reacting MnCl2 and NaBH4 in THF, the complex MnOBH4)2 (THF)3 was obtained and characterized by chemical analysis and physicochemical methods.

Mechanochemical synthesis of triphenylmethylium and triphenylcyclopropenylium tetrakis(pentafluorophenyl)borates

A possibility of application of mechanochemical method for the synthesis of triphenylmethylium and triphenylcyclopropenylium tetrakis(pentafluorophenyl)borates by the solvent-free reaction of solid starting compounds was studied. Some specific features of these reactions were discovered. Preparative methods for the mechanochemical synthesis of these salts were developed. This method makes the process shorter and excludes the use of solvents in the synthesis.

Self-propagating synthesis of chromium acetylacetonate

After preliminary mechanical activation a mixture of solid chromium(III) chloride and sodium acetylacetonate becomes capable of reacting to form chromium acetylacetonate. The reaction may be carried out in the mode of a self-propagating process.