| Author(s): |
Denis E. Bergeron; Orkid Coskuner; Jeffrey W. Hudgens; Carlos A. Gonzalez; |
| Title: |
Ligand Exchange Reactions in the Formation of Diphosphine-Protected Gold Clusters |
| Published: |
August 14, 2008 |
| Abstract: |
Electrospray ionization mass spectrometry is employed to study the formation of L3- and L5-protected gold clusters (L3 = 1,3-Bis(diphenylphosphino)propane; L5 = 1,5-Bis(diphenylphosphino)pentane), and it is found that molecular complexes in which Au+ is bound to at least one triphenylphosphine ligand (PPh3) act as precursors, while complexes in which Au+ is bound only to the bidentate diphosphine ligands act as reaction bottlenecks. Ligand exchange mechanisms and ion equilibria were established in the absence of a reducing agent, and a critical reaction was modeled with ab initio molecular dynamics simulations. The displacement of one PPh3 by L3 on [Au(PPh3)2]+ was studied with Car Parrinello molecular dynamics and transition path sampling. It is found that experiment and theory converge on a complete description of a reaction event critical in the synthesis of a particular set of monolayer protected nanoparticles. |
| Citation: |
Journal of Physical Chemistry C |
| Volume: |
112 |
| Issue: |
33 |
| Pages: |
pp. 12808 - 12814 |
| Keywords: |
Electrospray ionization; gold nanoparticle; Car-Parrinello molecular dynamics; monolayer protected gold cluster |
| Research Areas: |
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| PDF version: |
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