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

Published

August 14, 2008

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

Pub Type

Journals

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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 October 3, 2025)