Hydroxylamines as new decarbonylating reagents in the synthesis of metal carbonyl derivatives

Article abstract of DOI:10.1016/0022-328X(94)24747-7

Mononuclear and cluster carbonyl complexes react with amino functional compounds under mild conditions in the presence of H2O2 to form mixed amino carbonyl derivatives.It was found that a group of reactive species facilitating the process are hydroxylamines which arise in situ as a result of oxidation of amino compounds.On the basis of kinetic data and certain other measurements the mechanism of interaction of M(CO)6 (M = Cr, Mo, W) and NH2OH is proposed.This includes nucleophilic attack by NH2OH on a carbonyl carbon resulting in CO oxidation and CO2 elimination with simultaneous intramolecular movement of the amino group to the metal atom.The above mechanism is compared with that for the analogous reaction facilitated by Me3NO, studied earlier. Keywords: Chromium; Molybdenum; Tungsten; Osmium; Cluster; Hydroxylamine