A. P. Borisov

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.

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.

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.

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.

Preparation of calcium cyclopentadienyl complexes using calcium borohydride

Calcium borohydride reacts with sodium cyclopentadienyl compounds in tetrahydrofuran solution to give the corresponding calcium cyclopentadienyl complexes. The reaction proceeds easily and gives high yields.

Complexes of manganese borohydride with the borohydrides of organic cations

Conclusions1.Reaction of MnCBH4)2(THF)3 with tetrabutylammoniura and tetraphenylphosphonium borohydndes, and with tetraphenylphosphonium chloride, has given the compounds (Bu4N)[Mn(BH4)3], (Ph4P)[Mn(BH4)3], (Ph4P)[Mn(BH4)3(THF)], (Ph4P) [Mn(BH4)3Cl], and (Ph4P) [Mn(BH4)2Cl(THF)], which have been characterized by IR spectroscopy and thermogravimetric studies.2.The crystal and molecular structure of the manganese complex (Ph4P) [Mn(BH4)3−xClx (THF)] (x∼ 0.5) has been found.

Solid-state mechanochemical synthesis of tris(4-imino-2-pentanonato)chromium, Cr[CH3C(NH)CHC(O)CH3]3

Tris(4-imino-2-pentanonato)chromium was prepared by solid-state synthesis under conditions of mechanical activation of a mixture of chromium(III) chloride and sodium 4-imino-2-pentanonate and characterized by IR spectroscopy, X-ray diffraction, and electronic absorption spectroscopy.

ANIONIC ZIRCONIUM AND HAFNIUM BOROHYDRIDE COMPLEXES

Zirconium and hafnium tetrachlorides react with NaBH4, in dimethoxyethane (DME) to give [Na(DME)3][M(BH4)5]. These compounds react with Bu4NBH4 and Ph4PBH4 to give (R4E)[M(BH4)5]. Bidentate and tridentate BH4− occur in [M(BH4)5]− according to IR spectroscopy. Data from1H and1H-{11B} NMR spectra are consistent with intermolecular exchange of BH4 ligands in solutions of complexes (I)–(VI). The BH4groups and the bridging and terminal protons in each BH4 group equilibrate rapidly. Heating the complexes (I)–(VI) reduces the central atom, releases diborane, and decomposes the outer-sphere cation. The neutral borohydrides M(BH4)4, can be prepared by thermolysis of the sodium salts (I) and (II).