ATOM-TRANSFER REDOX REACTIONS OF NITRITE ANION WITH TRANSITION METAL CARBONYL CATIONS

Article abstract of DOI:10.1016/S0022-328X(00)98778-3

The reactions of several carbonyl cations with bis(triphenylphosphine)imminium nitrite under aprotic conditions have been studied using acetone as solvent.The trigonal-bipyramidal iron(0) and colbalt(I) cations ⁺, ⁺, ⁺ and ⁺ yielded four-coordinate iron(-II) and cobalt(-I) nitrosyl complexes Fe(NO)(N2C6H4COCH3-p)(CO)(PPh3), Fe(NO)2(CO)(PPh3), Fe(NO)2(PPh3)2, Co(NO)(CO)2(PPh3) and Co(NO)(CO)2(P(Bu-n)3) via a procedure which is much simpler than previous methods.The reaction involves an atom-transfer redox between nitrite and coordinated CO to yield the coordinated nitrosyl ligand and CO2.The related cation ⁺ did not react.The other cations investigated underwent decomposition and/or gave non-nitrosyl products with the exception of ⁺ which yielded an unstable blue nitrosyl which could not be characterised.A modification of the procedure employing Na(15)NO2 in the presence of a catalytic amount of crown ether was shown to be a very simple method for the preparation of 15N-labelled nitrosyls.The analogues reaction with arenediazotate anion did not lead to arenediazo complexes.