The new ferrocenic polyphosphines [C5Me3-1, 2-(PPh2) 2](C5H5) Fe 2,[C5Me3-1, 2-(PPh2) 2] 2Fe 3,[C5Me3-1, 2-(PPh2) 2][C5Me4 (PPh2)] Fe 4 and polythioethers [C5Me3-1, 2- (SCH2CH2CH3) 2] 2Fe 6 and [C5Me3-1, 2-(SCH2CH2CH3) 2](C5H5) Fe 7 have been prepared. The X-ray crystal structures of 3 and 6 have been determined. Some aspects of the reactivity of compounds 2, 3 and 4 are reported (P (III)→ P (V) transformation, ...