Phosphonothioate Hydrolysis
Turnover by Cp<sub>2</sub>MoCl<sub>2</sub> and Silver Nanoparticles
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Abstract
The metallocene bis(cyclopentadienyl)molybdenum(IV) dichloride
(Cp<sub>2</sub>MoCl<sub>2</sub>; Cp = η<sup>5</sup>-C<sub>5</sub>H<sub>5</sub>) 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 <sup>31</sup>P NMR studies on the reaction of <i>O</i>,<i>S</i>-diethyl phenylphosphonothioate (DEPP)
with Cp<sub>2</sub>MoCl<sub>2</sub> (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<sup>+</sup>(aq) ions present in the solution
that arise either from the slow dissolution of the nanoparticles or
from interactions with the Ag nanoparticle surface