Can the Stereogenic 1,1’‐Bi‐2‐naphtol Molecule Be Coordinated to W(VI) or Mo(VI) Peroxo Moieties?

Abstract

The reaction of 1,1’‐bi‐2‐naphtol, a well‐known stereogenic 1,4‐diol used in asymmetric synthesis, with molybdenum(VI) or tungsten(VI) oxoperoxo species at room temperature leads to the cleavage of the carbon‐carbon bond linking the two naphtol units with concomitant oxidation generating 2‐hydroxy‐1,4‐naphtoquinone. This later compound acts as a bidentate chelating ligand towards the d0 metal center resulting in an anionic complex, [M(C10H5O3) O(O2)2]− (M=Mo, W), that has been characterized by single crystal X‐ray diffraction and IR and Raman spectroscopies. The formation of this compound raises the question as whether or not 1,1’‐bi‐2‐naphtol can be coordinated to peroxo Mo(VI) or W(VI) centers without being oxidatively degraded.