Mono-oxygen donor

Primary amines are oxidized to the corresponding oximes. The sequence of reactions closely parallels the sequence observed with other mono oxygen donors, i.e., oxidation to alkyl hydroxylamines (V) followed by oxidation to alkylnitroso compounds (VI) which, via a prototropic shift, rearrange to the oximes (VII) ... 

Summarizing the information disclosed in the section above, one notes that polyoxometalates appear to be versatile oxidation catalysts capable of activating various mono-oxygen donors such as iodosobenzene, periodate, ozone, nitrous oxide, and sulfoxides. Some of these reactions are completely new from both a synthetic and mechanistic point of view. The various reaction pathways expressed are also rather unusual and point to the many options and reaction pathways available for oxidation catalyzed by polyoxometalates. 

Structural aspects and coordination chemistry of metal porphyrin complexes with emphasis on axial ligand binding to carbon donors and mono- and di-atomic nitrogen and oxygen donors. P. D. Smith, B. R. James and D. H. Dolphin, Coord. Chem. Rev., 1981,39, 31-75 (170). 

My co-worker J. Sedlmeier then held the view that the amine-containing iron carbonyl complexes were also ionic compounds (VII, 14, 21). Hence the compound Fe2(CO)4(en)3 (en= 1,2-ethylenediamine) was formulated as [Fe(en)3]2+[Fe(CO)4]2. Systematic investigations revealed that reactions of the iron carbonyls with other nitrogen and oxygen donors likewise involved valency disproportionation of the metal with concomitant formation of mono- and polynuclear carbonylferrates, viz., [Fe(CO)4]2, [Fe2(CO)8]2-, [Fe3(CO)n]2-. R. Werner (VII, 15, 17, 19, 20) even discovered and characterized compounds containing the tetranuclear anion [Fe4(CO)13]2, the first being that from pyridine and iron carbonyl, viz.,... 

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