Formation of transition metal-oxaziridines from molybdenum oxide(Et(2)dtc)(2)(THF)(2)iodine(2) and nitroso compounds

Mo2O3(Et2dtc)2(THF) 2I2 (1) reacts with a variety of oxygen atom donor substrates, X-O, such as pyridine-N-oxides, sulfoxides and nitrate to produce MoO2^2+ complexes and X by oxygen atom transfer. Results from kinetics studies indicate the formation of a (1)-substrate intermediate that decomposes to form the products. The lifetime of the intermediate apparently depends on the stability of the leaving group, X. Since the R-group in nitroso compounds, R-N=0, would not be stable leaving groups the (1)-nitroso complex might be expected to be quite long lived or even stable. Indeed, reaction of (1) with nitroso compounds such as nitrosobenzene produce stable molybdenum-oxaziridines which have been identified using 1H-NMR, IR and electronic spectral data. The use of these complexes in the mediation of allylic amination reactions was studied.