NEW 17 ELECTRON COMPLEXES OF IRON

One electron oxidation reactions are predicted forFe(C5H5)(dpe)X compounds according to cyclic voltammetry. These oxidations have been carried out using AgPF6 as an oxidant, and a number of 17e complexes of the formula [Fe(C5H5)(dpe)X]PF6 (X = Cl, Br, I, H, Me, SnMe3, CN, SCN (N bonded isomer), SPh) has been isolated. The compound [Fe(C5H5)(dpe)SPh]BF4 also is formed from addition of HBF4 to the appropriate 18 electron precursor, while addition of a potentially stronger oxidizing agent NOPF6 gives [Fe(C5H5)(dpe)NO](PF6)2. The compound [Fe(C5H5){P(OPh)3}2I]PF6 has been isolated. The 17e species Fe(C5H5)(dpe)S2O3 forms from [Fe(C5H5)(dpe)(MeCN)]PF6 and Na2S2O3. This may be the first organometallic compound having an S2O3 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). © 1979.