Abstract

Activation of the S-S bond in disulfides by the fragment CpFe(dppe) + produces the oxidized thiolate complexes [CpFe(dppe)-SR]PF 6, R = CH 3, C 3H 7, CH 2-C 6H 5, C 6H 5. With the bulky ( tBu) 2S 2 the unaltered disulfide complex [CpFe(dppe)S 2( tBu) 2]PF 6 was obtained. The reaction which yields the 17e - paramagnetic thiolate complexes occurs only in solvents with a high dielectric constant. Formation of diamagnetic [CpFe(dppe)S 2R 2]PF 6 complexes as the first step in the formation of the paramagnetic species [CpFe(dppe-SR]PF 6 is discussed.