Complexes of Rhodium(I) and Iridium(I) with the Chiral Tridentate Phosphane Pigiphos: Structure and Reactivity Studies

The chiral ferrocenyltriphosphane Pigiphos [bis{( S )‐1‐[( R )‐2‐(diphenylphosphanyl)ferrocenyl]ethyl}cyclohexylphosphane] forms four‐coordinate complexes with Ir I and Rh I . The tridentate ligand assumes different conformations in the derivatives [Rh(CO)(Pigiphos)]OTf ( 4 ) and [IrCl(Pigiphos)] ( 1b ), the latter also showing a drastic deviation from the square‐planar geometry. Reactivity studies have focussed on the more reactive 1b . The HCl and O 2 adducts have been characterized in solution. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)