Synthese neuer Phosphan- und Fluorophosphankomplexe durch Ligandmodifikation in der Koordinationssphäre von kationischen Cyclopentadienyleisen-bis(phosphan)-Komplexen / Synthesis of New Phosphane and Fluorophosphane Complexes by Ligand Modification in the Coordination Sphere of Cationic Cyclopentadienyliron Bis(phosphane) Complexes

Abstract

The reaction of nitrile solvate complexes [(C5H5)(P(OCH3)3)2(NCCH3)Fe]PF6 (Ia) and [(C5H5)(DPPE)(NCCH3)Fe]PF6 (Ib, DPPE = [(C6H5)2PCH2]2) with halogenophosphanes, -arsines or -stibines L′ afford the cationic complexes [(C5H5)(L2)(L′)Fe]PF6 (II, L2 = (P(OCH3)3)2, L′ = PCl3, P(CH3)Cl2, P(t-C4H9)Cl2, P(C6H5)Cl2, P(C6H5)2Cl, PBr3, AsCl3, SbCl3; III, L2 = DPPE, L′ = PCl3, AsCl3, SbCl3) in high yield. Spectroscopic data are given together with the characterization of [(C5H5)(P(OCH3)3)2(P(t-C4H9)Cl2)Fe]PF6 (IIc) by single crystals X-ray diffraction analysis. Through reduction of coordinated P– Cl ligands in selected complexes II and III complexes bearing PH3, P(C6H5)H2 and P(C6H5)2H ligands are available. With anhydrous KF in acetonitrile solution in the presence of dibenzo-18-crown-6, the coordinated P– Cl ligands in selected complexes II and HIII undergo Cl/F-exchange with formation of related complexes with P(CH3)ClF, P(CH3)F2, PF2Cl and PF3 ligands.