Phosphonothioate Hydrolysis Turnover by Cp₂MoCl₂ and Silver Nanoparticles

The metallocene bis­(cyclopentadienyl)­molybdenum­(IV) dichloride (Cp₂MoCl₂; Cp = η⁵-C₅H₅) is the first organometallic compound to promote the hydrolysis of phosphonothioates with selective P–S scission in a stoichiometric fashion. This report shows that silver nanoparticles capped with borohydride ions promote turnover in this hydrolytic process, as indicated by ³¹P NMR studies on the reaction of O,S-diethyl phenylphosphonothioate (DEPP) with Cp₂MoCl₂ (pH 7). This is the first example of the joint use of nanoparticles and molybdenum metallocenes to promote phosphonothioate hydrolysis. Initial results indicate the turnover may be due to free Ag⁺(aq) ions present in the solution that arise either from the slow dissolution of the nanoparticles or from interactions with the Ag nanoparticle surface.