The electrochemistry of the complex [Fe(CO)(2)(NO)(2)] and the IR and EPR spectra of the one-electron reduced [Fe(CO)(2)(NO)(2)](center dot-) and one-electron oxidised species [Fe(CO)(2)(NO)(2)](center dot+) reveal mainly NO-centred spin density for the unpaired electron. The results are discussed in term of oxidation states. Furthermore, the parent complex was investigated for light-induced linkage isomerisation using IR spectroscopy. Thermally and optically reversible generation of a new species identified by new vibrational bands is interpreted in terms of photoinduced nitrosyl linkage isomers. (C) 2010 Elsevier Ltd. All rights reserved.