Sterically demanding diphosphonite ligands - Synthesis and application in nickel-catalyzed isomerization of 2-methyl-3-butenenitrile

Abstract

The synthesis of a novel class of sterically demanding diphosphonites 1-8, based on rigid backbones, is described. The starting materials are all commercially available and the methodology allows for a modular approach. All ligands have been fully characterized, including an X-ray crystal structure for compound 1, 4,5-bis{di[(2-terr-butyl)phenyl]phosphonito}-9,9-dimethylxanthene. The coordination of these diphosphonite ligands towards Ni(II) and Ni(0) precursors is investigated, both by NMR spectroscopy as well as X-ray crystallography and compared with the behaviour of diphosphine ligands such as Xantphos. The molecular structure for complex 9, trans-[NiBr2(1)] is described in detail. The nickel-catalyzed isomerization of 2-methyl-3- butenenitrile to 3-pentenenitrile is studied, a relevant step in the industrially important hydrocyanation of butadiene (the DuPont adiponitrile process). Good activities and selectivities to the desired 3-pentenenitrile are obtained in this reversible C-C bond activation reaction.