[3+2] cycloaddition reaction of metallacyclopropene with nitrosonium ion: isolation of aromatic metallaisoxazole

The [3+2] cycloaddition of metallacyclopropene with nitrosonium ion gives the first aromatic osmaisoxazole-fused osmapentalene.

Nitrosonium ion catalysis: aerobic, metal-free cross-dehydrogenative carbon–heteroatom bond formation

Catalytic cross-dehydrogenative coupling of heteroarenes with thiophenols and phenothiazines has been developed under mild and environmentally benign reaction conditions.

Nitrosonium-Mediated Phenol–Arene Cross-Coupling Involving Direct C–H Activation

The nitrosonium ion (NO+) is a highly versatile nitration and nitrosation reagent, as well as a strong one-electron oxidant. Herein, we describe an environmentally benign and mild method for the in situ formation of NO+ from readily available inorganic nitrate salts, i.e. lithium nitrate, through a finely tuned interplay between formic acid and MeOH, which are used as the solvent system. This methodology was applied to the NO+-induced oxidative C–H activation of methoxy-substituted phenols, which are versatile lignin-derived aromatic feedstocks, to achieve C–C cross-coupling reactions with arenes. The regeneration of NO+ by atmospheric molecular oxygen enables substoichiometric use of the nitrate.

An isoelectronic NO dioxygenase reaction using a nonheme iron(iii)-peroxo complex and nitrosonium ion

Reaction of a nonheme iron(iii)-peroxo complex, [FeIII(14-TMC)(O2)]+, with NO+ affords an iron(iv)-oxo complex, [FeIV(14-TMC)(O)]2+, and nitrogen dioxide (NO2), followed by conversion to the nitrato complex, [FeIII(14-TMC)(NO3)(F)]+.