Knowledge Bank

Reduction of CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ is an essential step in its chemical conversion from a greenhouse gas to useable fuel stocks, but is energetically unfavorable. Association with anions has been shown to facilitate partial charge transfer to a target CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ molecule, which could be a significant step towards CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ recycling. However there is still much uncertainty in the role of solvent effects on these chemical processes. We present infrared spectra of [Ag$\cdot$(CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$)]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ ($n=2-11$) to elucidate the nature of the charge carrier in the cluster, the effects of solvation on the charge distribution and the amount of reductive activation of CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$ in the presence of a Ag anion. The structures of the [Ag$\cdot$(CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$)]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ clusters are discussed in the framework of density functional theory. We compare and contrast the findings of [Ag$\cdot$(CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$)]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ to those recently published on [Au$\cdot$(CO$\mathrm{<mrow\; data-mjx-texclass="ORD">2</mrow>}$)]$\mathrm{<mrow\; data-mjx-texclass="ORD">-</mrow>}$ [1]. 1. B.J. Knurr and J.M. Weber, J. Amer. Chem. Soc., 134 (2012) 18804-18808.