Exogenous nitrile substrate hydroxylation by a new dicopper-hydroperoxide complex

A dicopper(I)/phenol-ligand complex in RCN solvents reacts with O2 producing a mu-1,1-hydroperoxo dicopper(II) species. Subsequent thermal transformation results in nitrile hydroxylation and elimination of cyanide, as revealed by the isolation in comparable yields of (i) a cyanide-bridged tetranuclear cluster complex and (ii) benzaldehyde (for R = PhCH2); 18O labeling confirms that the PhC(O)H oxygen atom derives from O2.     

Dicopper peroxo complexes: low temperature stopped-flow reaction kinetics of [(BQPA)CuI]+ and [(Me2-TMPA)CuI]+

In the last 20 years, the reaction of many different CuI complexes and with dioxygen has been described. There is quite a big variety in their coordination geometry and most of them have been characterized by X-ray crystallography. Beyond structural information, stopped-flow kinetics experiments have provided additional mechanistic insights. In the particular systems [(BQPA)CuI]+ and [(Me2-TMPA)CuI]+ a new equilibrium between the two species trans-mu-1,2-peroxo and bis-mu-oxo is demonstrated. In the case of [(BQPA)CuI]+ the two species are in an equilibrium, presumably via the transient superoxo species. The reaction of [(Me2-TMPA)CuI]+ with dioxygen leads to the parallel formation of both species. The kinetically preferred trans-mu-peroxo species is then isomerised to the thermodynamically more stable bis-mu-oxo species.     

Universal expansion of three-particle distribution function

Computing Center, Siberian Branch of the USSR Academy of Sciences, Krasnoyarsk. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 88, No. 3, pp. 430–441, September, 1991.     

Glycosides ofPatrinia sibirica. II

Chemistry of Natural Compounds - It has been established that two trisaccharide chains are present in sibiroside C, one combined with the 3-hydroxyl and the other with the 28-carboxyl of...