Investingation of the reaction of metal-nitrosyl complexes. I. New nitrosolysis reaction of cycloalkanones using sodium pentacyanonitrosylferrate(II).

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Cycloalkanones reacted with sodium pentacyanonitrosylferrate(II) (NP) to give red-brown or red-violet colored complexes under an alkaline condition. The solvolysis of the complexes gave ω-(hydroxyimino)alkanoic acids under a hot alkaline condition and gave ω-cyanoalkanoic acids or their esters in an acidic condition in good yields. These Products correspond to nitrosolysis products of cycloalkanones. The reaction mechanism was invesigated by use of <SUP>15</SUP>N labeled NP. The complex was formed initially by an electrophilic attack of the nitrosyl ligand of NP to the active methylene of the cycloalkanone. Then a C–C bond cleavage of the resulting ligand, 2-(hydroxyimino) cycloalkanone, occurred by an action of the solvent species under the influence of the central ferrate ion. The solvolysis of the ligand occurred through Beckmann fission by an action of the acid in the coordination sphere.