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Ligand Exchange Reactions in the Formation of Diphosphine-Protected Gold Clusters

Published

Author(s)

Denis E. Bergeron, Orkid Coskuner, Jeffrey W. Hudgens, Carlos A. Gonzalez

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

Keywords

Electrospray ionization, gold nanoparticle, Car-Parrinello molecular dynamics, monolayer protected gold cluster

Citation

Bergeron, D. , Coskuner, O. , Hudgens, J. and Gonzalez, C. (2008), Ligand Exchange Reactions in the Formation of Diphosphine-Protected Gold Clusters, Journal of Physical Chemistry C, [online], https://tsapps.nist.gov/publication/get_pdf.cfm?pub_id=832202 (Accessed November 28, 2022)
Created August 14, 2008, Updated February 17, 2017