A new property of geminal bishydroperoxides: Hydrolysis with the removal of hydroperoxide groups to form a ketone

A new property of geminal bishydroperoxide was discovered: the ability to hydrolyze in acid medium in the presence of hydrogen peroxide with the formation of ketones. The most resistant to hydrolysis are the cyclic C₆-bishydroperoxydes: at room temperature within one day they are practically not hydrolyzed; less stable is bishydroperoxycycloheptane (C₇): in a day its one fifth part is hydrolyzed. Bishydroperoxydes with the cycles of C₈ and C₁₂ for the same time hydrolyzed to 80 and 90% respectively. Of the two linear bishydroperoxydes, 2,2-dihydroperoxydecane, with sterically unhindered center, is more resistant to hydrolysis than 6,6-dihydroperoxyundecane.     

η3-Propargyl complexes of molybdenum, tungsten, and rhenium

The reactions of the Me _n C₆H_6−n M(CO)₃ (M=Cr, Mo, W;n=3, 5, 6) and C₅R₅M(CO)₃ (M=Mn, Re; R=H, Me) complexes with propargyl alcohol in acidic media under UV irradiation were studied. Novel Me _n C₆H_6−n M(CO)₂(η³-C₃H₃)BF₄ (M=Mo, W;n=3, 5, 6) and C₅R₅Re(CO)₂(η³-C₃H₃)CF₃SO₃ complexes with the 3ē-propargyl ligand were synthesized, and their properties compared with those of similar η³-allyl derivatives. The structure and dynamic propeties of the compounds obtained are discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1796–1803, September, 1999.     

Electron transfer-induced replacement of carbonyl ligands in cobalt clusters

Russian Chemical Bulletin -     

Molecular structure of an areneolefindicarbonyl-chromium chelate complex with (2,5-dimethylbenzyl)-allyl ether as the chelate ligand

(2,5-Dimethylbenzyl)allyl ether produces two diastereomeric pairs of enantiomers with _η⁸ coordination of the Cr(CO)₂ group; the structure of the principal enantiomeric pair is established by complete X-ray analysis.     

Synthesis and isomerism of methoxyallene derivatives of cymantrene

All of the three isomeric complexes possible for monosubstituted allenes were obtained by the interaction of 1-methoxypropadiene with CpMn(CO)₃ under UV irradiation or with CpMn(CO)₂(THF). The complexes were isolated as individual compounds and characterized by IR and¹H and¹³C NMR spectroscopy.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1488–1490, August, 1994.     

Stable 17-electron manganese complexes in the synthesis of macromolecules

Radical polymerization of methyl methacrylate and styrene in the presence of several cyclopentadienyl manganese dicarbonyl derivatives was studied. The influence of the molecular structure of the complexes on the molecular-weight characteristics of the macromolecules was estimated. Quantum chemical modeling of the initial polymerization step with participation of these complexes was performed.     

An atomic-force microscopy study of the formation of vinyl and acryl graft polymers on a polypropylene film surface

Changes in the surface structure of oriented polypropylene (PP) films in conditions of graft copolymerization of acrylamide, vinylpyridine, and styrene on a PP surface preliminary subjected to plasmochemical activation in oxygen plasma or in a plasma-electrolyte solution system are investigated by atomic-force microscopy. It is shown that the latter soft conditions of activation are superior to the hard conditions with oxygen plasma in retaining original lamellar structure of oriented PP films. It is established that the subsequent graft copolymerization of the vinyl and acryl monomers on the PP surface yields amorphous phases of respective polymers.