Cerium(III) Phosphinate and Cerium(IV) Phosphostibonate Acting as Catalysts for Mild, Selective Sulfoxidation.

A Ce(III) phosphinate and a Ce(IV) phosphostibonate have been assembled by the reaction of a phosphinic acid and phosphostibonate with Ce(III) salts. Single crystal X-ray diffraction (SCXRD) studies reveal the formation of a rare triangular Ce(III) oxo-cluster [Ce(PhCHPO)]Cl(CHOH)(HO)] () and a fascinating hexanuclear oxo-cluster containing Ce(IV) ions [Ce (-ClCHSb)(μ-O)(μ-O)(-BuPO)(μ-OCH)] (). The molecular architecture of showcased an interesting correlation with platonic solids, wherein the Ce(IV), Sb(V), and P(V) ions were found to be present in vertices of an octahedron, a tetrahedron, and a cube, respectively. Under mild conditions, and exhibited the capability to act as catalysts for sulfoxidation in the presence of hydrogen peroxide, with acting as a homogeneous catalyst and acting as a heterogeneous catalyst. Both and showed high conversion for various substrates, with showing moderate selectivity while showcased high selectivity. Moreover and catalyzed the oxidation of 2-chloroethyl ethyl sulfide (CEES) to nontoxic 2-chloroethyl ethyl sulfoxide (CEESO) with high selectivity.