Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II)

The aquapentacyanoferrate(II) ion, Fe(II)(CN)(5)H(2)O](3-), catalyzes the disproportionation reaction of O-methylhydroxylamine, NH(2)OCH(3), with stoichiometry 3NH(2)OCH(3) → NH(3) + N(2) + 3CH(3)OH. Kinetic and spectroscopic evidence support an initial N coordination of NH(2)OCH(3) to Fe(II)(CN)(5)H(2)O](3-) followed by a homolytic scission leading to radicals Fe(II)(CN)(5)(?)NH(2)](3-) (a precursor of Fe(III) centers and bound NH(3)) and free methoxyl, CH(3)O(?), thus establishing a radical path leading to N-methoxyamino ((?)NHOCH(3)) and 1,2-dimethoxyhydrazine, (NHOCH(3))(2). The latter species is moderately stable and proposed to be the precursor of N(2) and most of the generated CH(3)OH. Intermediate Fe(III)(CN)(5)L](2-) complexes (L = NH(3), H(2)O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by Fe(II)(CN)(5)L](3-). Free or bound NH(2)OCH(3) may act as reductants of Fe(III)(CN)(5)L](2-), thus regenerating active sites. At increasing concentrations of NH(2)OCH(3) a coordinated diazene species emerges, Fe(II)(CN)(5)N(2)H(2)](3-), which is consumed by the oxidizing CH(3)O(?), giving N(2) and CH(3)OH. Another side reaction forms Fe(II)(CN)(5)N(O)CH(3)](3-), an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, Fe(II)(CN)(5)NO](2-). The latter is a final oxidation product with a significant conversion of the initial Fe(II)(CN)(5)H(2)O](3-) complex. The side reaction partially blocks the Fe(II)-aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the Fe(II)-NO(+) bonds.