OXIDATIVE ADDITION OF DISULFIDES TO THE FRAGMENT CPFE(DPPE)(- STERIC AND DIELECTRIC MEDIUM CONTROL ON THE REACTION() )

Activation of the S-S bond in disulfides by the fragment CpFe(dppe)(+) produces the oxidized thiolate complexes [CpFe(dppe)-SR]PF6, R = CH3, C3H7, CH2-C6H5, C6H5. With the bulky ((t)Bu)(2)S-2 the unaltered disu lfide complex [CpFe(dppe)S-2((t)Bu)(2)]PF6 was obtained. The reaction which yields the 17e(-) paramagnetic thiolate complexes occurs only in solvents with a high dielectric constant. Formation of diamagnetic [C pFe(dppe)S(2)R(2)]PF6 complexes as the first step in the formation of the paramagnetic species [CpFe(dppe-SR]PF6 is discussed.