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Competition Between Thiol and Phosphine Ligands During the Synthesis of Au Nanoclusters

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Abstract

Reduction of a mixture of Ph3PAuCl and CH3(CH2)5SH with NaBH4 yields predominately phosphine encapsulated nanoclusters with Au cores <1 nm, similar to the product isolated when the alkane thiol is not present in the reaction. When Et3N is added to a solution of Ph3PAuCl and CH3(CH2)5SH, a Au–S bond is formed, and the subsequent reduction of this thiolate results in the formation of >2 nm core thiol encapsulated Au nanoclusters as the majority product. This latter reduction has been examined in more detail through in situ 31P NMR experiments, and a solution exchange reaction is observed wherein the PPh3 generated by the reduction displaces thiol from the surface of the nanocluster product. This thiol displacement occurs with loss of a Au atom from the nanocluster core, as observed by NMR.

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Notes

  1. The small shift in position of the Ph3PO signal is believed to be due to its interaction with one of the components of the reaction mixture. When the samples were isolated and run locked in CDCl3, this signal returned to 29 δ.

  2. See supporting information.

  3. Ph3P oxidizes slowly on standing in air in CDCl3 solvent to form Ph3PO, however control experiments indicate this process alone cannot account for the amount of Ph3PO seen in Fig. 8.

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Acknowledgments

The Office of Naval Research (ONR) is acknowledged for financial support of this work.

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  1. Naval Research Laboratory, Washington, DC, 20375, USA

    Edward E. Foos, Mark E. Twigg, Arthur W. Snow & Mario G. Ancona

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  1. Edward E. Foos
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  2. Mark E. Twigg
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Correspondence to Edward E. Foos.

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Foos, E.E., Twigg, M.E., Snow, A.W. et al. Competition Between Thiol and Phosphine Ligands During the Synthesis of Au Nanoclusters. J Clust Sci 19, 573–589 (2008). https://doi.org/10.1007/s10876-008-0205-6

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