ADDITION AND SUBSTITUTION-REACTIONS OF FE(CO)3[FE(CO)3+CH+CPH+S]

The compound {A figure is presented} (1) reacts with the organometallic fragments "Pt(PPh3)2", "Fe(CO)n" (n = 2, 3) or "CoC5H5", under insertion of these fragments into the sulfur carbon bond of 1 to give {A figure is presented} (3) or the triple-decker compounds {A figure is presented} (2), and Fe2(CO)5Co2(C5H5)2 (HCCPh)(S) (5), respectively. Reaction of 1 with two-electron donor ligands L yields the substitution products {A figure is presented} (6a, 6b) and {A figure is presented} (7a, 7b) (6a, 7a: L = P(OCH3)3, 6b, 7b: L = PPh3). Dynamic 1H and 31P NMR spectroscopy of the compounds 6a and 7a documents a rapid exchange between the two iron centers. The synthesis and properties of the compounds 3, 5-7b are described. The bonding in the structures of 3, 6a, 7a and 7b is best described in terms of the π-coordinated heterometallacycles. © 1990.