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

Abstract

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)Cl2] [dppdtbpf = 1‐diphenylphosphino‐1′‐(di‐tert‐butylphosphino)ferrocene], [Zn(dippfO2)Cl2] [dippf = 1,1′‐bis(diisopropylphosphino)ferrocene], [Zn(dtbpfO2)Cl2] [dtbpf = 1,1′‐bis(di‐tert‐butylphosphino)ferrocene], and [Zn(4S)Cl2] (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‐C6H4Br)3][B(C6F5)4] result in the loss of a chlorido ligand to form [Au2(µ‐Cl)(PP)][B(C6F5)4]. The structures of [(AuCl)2(dtbpf)] and [Au2(µ‐Cl)(dtbpf)][B(C6F5)4] were determined, and [Au2(µ‐Cl)(dtbpf)]+ displays a weak Au–Au interaction that is not present in [(AuCl)2(dtbpf)]. The oxidative electrochemistry of [Au2(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.