A dual
optimization approach to nanoparticle catalysis is reported
in which both the composition of a bimetallic nanoparticle and the
electronic properties of the supporting polystyrene-based polymer
can be varied to optimize reactivity and chemoselectivity in nitroarene
reductions. Ruthenium–cobalt nanoparticles supported on polystyrene
are shown to catalyze nitroarene reductions at room temperature with
exceptional activity, as compared with monometallic ruthenium catalysts.
Both the identity of the second metal and the M1/M2 ratio show a profound effect on the chemoselectivity of nitroarene
reductions. These polymer-supported bimetallic catalysts are shown
to react with nearly complete chemoselectivity for nitro group reduction
over a variety of easily reducible functional groups. The electronic
properties of the supporting polymer also have a significant impact
on catalysis, in which electron-deficient polystyrenes enable 100%
conversion to the aniline product in just 20 min at room temperature.
Polymer effects are also shown to influence the mechanism of the reduction
reaction, in addition to accelerating the rate, confirming the impact
of the polymer structure on catalytic efficiency. These catalysts
are easily prepared in a single step from commercial materials and
can be readily recycled without loss of activity.
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