Oxygen at low temperature

Of the substrates that have worked well, let us first illustrate the 7-alkylidene-2,3-dioxabicyclo[2.2.1]heptane system 10. It was known that fulvenes react with singlet oxygen at low temperatures to afford the corresponding endoperoxides however, attempts to isolate these labile compounds led to decomposition, although NMR identification was possible at —70 °C 19>. When reduction of the singlet oxygenates with diimide was performed at —50 °C, the bicyclic peroxides 10 were obtained in high yield (Eq. 7) 20). 

The lactone-peroxides 17 are derived from the corresponding ot-pyrones. Singlet oxygenation at low temperature affords the unstable a-pyrone endoperoxides which, on warming up, readily decarboxylate into 1,2-diacylethylenes. However, subambient diimide reduction leads to the desired lactone peroxides 17 (Eq. 12)29). 

Action of oxygen at low temperature on the phosphine produces an explosive product. 

Bec, N., Gorren, A. C., Voelker, C., Mayer, B., Lange, R., Reaction of neuronal nitric-oxide synthase with oxygen at low temperature. Evidence for reductive activation of the oxy-ferrous complex by tetrahydrobiopterin, J. Biol. Chem. 273 (1998), p. 13502-13508... 

The price of the oxidation equivalent varies with the reagent [288]. Oxygen in air is the cheapest, followed by chlorine, electricity, hydrogen peroxide and finally ozone. Oxydation with oxygen at low temperature is only feasible biologically. Chlorine often forms very stable, highly toxic chlorinated compounds, which often limits its use. 

Iron(II) meso-tetrakis(2,4,6-trimethoxyphenyl)porphyrin and the triethoxy analogue have been synthesized by Vaska. These are different to the capped and picket fence porphyrins in that both sides of the porphyrin are sterically hindered. Dioxygen uptake by these iron(II) porphyrins at 25 °C in solution was found to be partially reversible. La Mar and co-workers166 have shown that the porphyrins Fe[T(2,4,6-OMe)3PP], Fe[T(2,4,6-OEt)3PP] and Fe[TpivPP] take up oxygen at low temperatures, in the absence of a base such as Melm or pyridine, to give dioxygen adducts of the... 

These ozonides can be prepared by photosensitized oxidation of suitably substituted heterocycles with singlet oxygen at low temperatures. The dye sensitizers are usually Methylene Blue, Rose Bengal, tetraphenylporphyrin, or 9,10-dicyanoanthracene. 

The electron affinities of clusters behave in a similar manner. This fact, undoubtedly, has a role to play in the chemistry exhibited by nanometals that has been reported in the literature recently. For example, it has been shown that Au atoms (Gold is a noble metal in the bulk state) supported on a TiOa substrate shows a marked size effect in their ability to oxidize the diatomic gas CO to CO2 via a mechanism involving O2 dissociative chemisorption and CO adsorption (Valden et al., 1998). Small Ni particles have also been found to dissociate CO (Doering et al., 1982). Smaller nanoparticles of Ag can dissociate molecular oxygen to atomic oxygen at low temperatures, whereas in the bulk state, the species adsorbed on the Ag surface is O2 (Rao et al., 1992). 

Pure hydroxylamine or its aqueous solutions can be stored for several weeks in the absence of oxygen at low temperatures. 

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