Synthesis of N-acryloyloxyethylacrylamide

Russian Journal of Organic Chemistry -     

Theoretical study of isomerization of molecules of salts and ion-molecule complexes of lithium of the type LiAB+→ABLi+ (AB=SiN−, AlO−, SiP−, AlS−, SiO,AlF, P2, SiS,AlCl)

Institute of Chemical Problems, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 30, No. 1, pp. 18–28, January–February, 1989.     

Asymmetric terminal ligation on substituted sites in a disorder-free Keggin anion, [beta-SiFe2W10O36(OH)2(H2O)Cl]5-

A new monomeric diiron beta-Keggin derivative, [(CH3)2NH2]5[beta-SiFe2W10O36(OH)2(H2O)Cl].7H2O (1) with non-adjacent substituted sites has been obtained in good yield by reaction of Fe(III) cations with [gamma-SiW10O36]8- in aqueous solution. The use of hydrogen bonding counter-cations produced a disorder-free polyanion. This situation facilitates unequivocal identification of the terminal ligands on Fe atoms and interpretation of the magnetic properties, which are also addressed by DFT calculations. Electrochemical studies establish that 1 can be step-wise reduced by two electrons and then reversibly oxidized.     

Molecular structure of a benzoic acid adduct of zinc benzoate dihydrate — [Zn(C6H5COO)2·2H2O]2C6H5COOH

Institute of Inorganic and Physical Chemistry, Azerbaijan Academy of Sciences. Translated from Zhurnal Strukturnoi Khimii, Vol. 33, No. 6, pp. 203–207, November–December, 1992.     

Insights into the structure and reactivity of acylperoxo complexes in the Kochi-Jacobsen-Katsuki catalytic system. A density functional study

Structural properties of the acylperoxo complexes [(Salen)Mn(III)RCO(3)] (2) and [(Salen)Mn(IV)RCO(3)] (3), the critical intermediates in the Kochi-Jacobsen-Katsuki reaction utilizing organic peracids or O(2)/aldehydes as oxygen source, have been studied with the density functional theory. Four distinct isomers, cis(O,N), cis(N,O), cis(N,N), and trans, of these complexes have been located. The isomer 2-cis(O,N) in its quintet ground state, and nearly degenerate isomers 3-cis(O,N) and 3-cis(N,O) in their quartet ground states are found to be the lowest in energy among the other isomers. The O-O bond cleavage in the cis(O,N), cis(N,O), and trans isomers of 2 and 3 has been elucidated. In complex 3, the O-O bond is inert. On the contrary, in complex 2, the O-O bond cleaves via two distinct pathways. The first pathway occurs exclusively on the quintet potential energy surface (PES) and corresponds to heterolytic O-O bond scission coupled with insertion of an oxygen atom into an Mn-N(Salen) bond to form 2-N-oxo species; this pathway has the lowest barrier of 14.9 kcal/mol and is 15.6 kcal/mol exothermic. The second pathway is tentatively a spin crossover pathway. In particular, for 2-cis(O,N) and 2-cis(N,O) the second pathway proceeds through a crucial minimum on the seam of crossing (MSX) between the quintet and triplet PESs followed by heterolytic O-O cleavage on the triplet PES, and produces unusual triplet 2-cis(O,N)- and 2-cis(N,O)-oxo ([(Salen)Mn(V)(O)RCO(2)]) species; this pathway requires 12.8 kcal/mol and is 1.4 kcal/mol endothermic. In contrast, for the 2-trans isomer, spin crossing is less crucial and the O-O cleavage proceeds homolytically to generate 2-trans-oxo [(Salen)Mn(IV)(O)] species with RCO(2) radical; this pathway, however, cannot compete with that in 2-cis because it needs 21.9 kcal/mol for activation and is 15.3 kcal/mol endothermic. In summary, the O-O cleavage occurs predominantly in the 2-cis complexes, and may proceed either through pure high spin or spin crossover heterolytic pathway to produce 2-cis-oxo and 2-N-oxo species.     

ESR studies of Mo?Ti oxide catalysts

According to ESR studies on mixed⁹⁵Mo-enriched Mo–Ti oxide systems, different types of Mo⁵⁺ ions and their formation conditions in these systems have been established.

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Mo–Ti , ⁹⁵Mo. Mo⁵⁺ .