Late Transition Metal Compounds with 1,1′‐Bis(phosphino)ferrocene Ligands

The syntheses of several new zinc compounds with 1,1′‐bis(phosphino)ferrocene ligands and their phosphine chalcogenide derivatives are reported. The X‐ray crystal structures of [Zn(dppdtbpf)Cl 2 ] [dppdtbpf = 1‐diphenylphosphino‐1′‐(di‐ tert ‐butylphosphino)ferrocene], [Zn(dippfO 2 )Cl 2 ] [dippf = 1,1′‐bis(diisopropylphosphino)ferrocene], [Zn(dtbpfO 2 )Cl 2 ] [dtbpf = 1,1′‐bis(di‐ tert ‐butylphosphino)ferrocene], and [Zn( 4 S)Cl 2 ] ( 4 = dppdtbpf) were determined. The oxidative electrochemistry of the zinc compounds was examined and typically produced irreversible oxidations. The reactions of [(AuCl) 2 (PP)] [PP = 1,1′‐bis(diphenylphosphino)ferrocene (dppf), dtbpf, or dppdtbpf] with [N( p ‐C 6 H 4 Br) 3 ][B(C 6 F 5 ) 4 ] result in the loss of a chlorido ligand to form [Au 2 (µ‐Cl)(PP)][B(C 6 F 5 ) 4 ]. The structures of [(AuCl) 2 (dtbpf)] and [Au 2 (µ‐Cl)(dtbpf)][B(C 6 F 5 ) 4 ] were determined, and [Au 2 (µ‐Cl)(dtbpf)] + displays a weak Au–Au interaction that is not present in [(AuCl) 2 (dtbpf)]. The oxidative electrochemistry of [Au 2 (µ‐Cl)(PP)] + displays two reversible waves, the first of which occurs at a potential similar to those of the corresponding [(AuCl) 2 (PP)] species.