Synthesis and structural characterization of Groups 10 and 11 mononuclear fluoroaryloxide complexes

Abstract

A study of four late-transition metal fluoroaryloxide (OAr F or OAr′) complexes is presented including X-ray crystallography, polynuclear solution NMR spectroscopy, UV–Vis spectroscopy and elemental analyses. The study includes three new compounds: [(Ph 3P) 2Ni(OAr F) 2] ( 1a), [(Ph 3P) 2Ni(OAr′) 2] ( 1b), [(COD)Pt(OAr F) 2] ( 2) and one compound whose synthesis and elemental analysis were reported previously: [(Ph 3P)Au(OAr F)] ( 3). These compounds represent the common L 2MX 2 ( 1a, 1b, 2) and LMX ( 3) ligand classes in Groups 10 and 11, respectively, but with an uncommon ligand type, the monodentate phenoxide. In the solid state, compounds 1a and 1b exhibit square-planar geometry at nickel with trans phosphines in each case. In solution, these nickel compounds slowly decompose in CH 2Cl 2. Compound 2 is quite stable in solution at room temperature with the two phenoxide ligands cis to one another in the solid state. Compound 3 has a virtually linear geometry at the gold center and is stable in the solid state in the dark but decomposes slowly in solution in the light. Comparison of these four fluoroaryloxide compounds with the protio analogs (or attempts to make such compounds) demonstrate the greater stability to reduction of late-metal aryloxide complexes with highly electron-withdrawing substituents on the phenoxide rings.