A ferrocenyl P/NNN hybrid ligand for binding soft/hard metal pairs

The ferrocene-linked P/NNN hybrid ligand 1-diphenylphosphino-1′-dipicolylaminomethylferrocene (FcPN3, 1) was synthesized and bound to a variety of transition metal ions. Treatment of 1 with (tht)AuCl afforded the P-bound gold(I) chloride complex [FcPN3AuCl] (2), treatment with ZnCl2 afforded the N,N,N-bound zinc(II) chloride complex, [FcPN3ZnCl2] (3), and treatment with [Cu(MeCN)4]OTf (OTf– = trifluoromethanesulfonate) afforded the [FcPN3Cu]OTf ion pair (4), where Cu(I) interacts with both the diphenylphosphino and the dipicolylaminomethyl fragments. Complexes 1–4 were characterized by NMR spectroscopy and the molecular structures were determined by X-ray crystallography. The heterometallic complexes [FcPN3(AuCl)(ZnCl2)] (5) and [FcPN3(AuCl)CuOTf] (6) were also synthesized and characterized by 1H and 31P NMR spectroscopy and mass spectrometry.