One electron oxidation reactions are predicted forFe(C 5H 5)(dpe)X compounds according to cyclic voltammetry. These oxidations have been carried out using AgPF 6 as an oxidant, and a number of 17e complexes of the formula [Fe(C 5H 5)(dpe)X]PF 6 (X = Cl, Br, I, H, Me, SnMe 3, CN, SCN (N bonded isomer), SPh) has been isolated. The compound [Fe(C 5H 5)(dpe)SPh]BF 4 also is formed from addition of HBF 4 to the appropriate 18 electron precursor, while addition of a potentially stronger oxidizing agent NOPF 6 gives [Fe(C 5H 5)(dpe)NO](PF 6) 2. The compound [Fe(C 5H 5){P(OPh) 3} 2I]PF 6 has been isolated. The 17e species Fe(C 5H 5)(dpe)S 2O 3 forms from [Fe(C 5H 5)(dpe)(MeCN)]PF 6 and Na 2S 2O 3. This may be the first organometallic compound having an S 2O 3 ligand. The 17e compounds are paramagnetic, with all but the CN compound having magnetic moments corresponding to oneunpaired electron; the magnetic moment of the CN − compound is abnormally low (0.55 BM).