文摘
We have investigated the gas-phase reactivity of silver clusters with ethanethiol in a fast-flow tube reactor. The primary cluster products observed in this reaction are Agub>nub>SHup>鈥?/sup> and Agub>nub>SHub>2ub>up>鈥?/sup>, indicating C鈥揝 bond activation, together with interesting byproducts Hub>3ub>Sup>鈥?/sup> and (Hub>3ub>S)ub>2ub>up>鈥?/sup>. Agub>nub>up>鈥?/sup> clusters with an odd number of valence electrons (n = even) were observed to be more reactive than those with an even number of electrons鈥攁 feature previously only observed in the reactivity of Agub>nub>up>鈥?/sup> with triplet oxygen, indicating that radical active sites play a role in their reactivity. Furthermore, the reactivity dramatically increases with large flow rate of ethanethiol being introduced in the flow tube. Theoretical investigations on the reactivity of Agub>13ub>up>鈥?/sup> and Agub>8ub>up>鈥?/sup> with ethanethiol indicate that both Agub>13ub>up>鈥?/sup> and Agub>8ub>up>鈥?/sup> face significant barriers to reactivity with a single ethanethiol molecule. However, Agub>8ub>up>鈥?/sup> reacts readily in a cooperative reaction with two ethanethiol molecules, consistent with the dramatic increase in reactivity with a large flow rate. Further hydrogen-transfer reactions may then release an ethylene molecule or an ethyl radical resulting in the observed Agub>nub>SHup>鈥?/sup> species.