Preparation and characterization of 4-dimethylaminopyridine-stabilized palladium nanoparticles.
4-Dimethylaminopyridine (DMAP)-stabilized palladium nanoparticles with a mean diameter of 3.4 +/- 0.5 nm are prepared from the aqueous phase reduction of Na2PdCl4 using NaBH4 in the presence of DMAP. TEM and UV-vis spectroscopy characterization of the nanoparticle dispersion shows no obvious change in the nanoparticles several months after preparation. 1H NMR spectroscopy of the nanoparticles shows that the nanoparticle dispersion also contains a boron/DMAP complex and two palladium/DMAP complexes. One of the palladium complexes crystallizes out of the dispersion and is identified as Pd(DMAP)4(OH)2 by X-ray crystallography. Following extensive analysis, it is believed that the palladium/DMAP complexes are formed following the oxidation of the palladium nanoparticles. The prepared nanoparticle dispersion promotes selective hydrogen/deuterium (H/D) exchange on the carbon atoms alpha to the endocyclic nitrogen atom on the DMAP-stabilizing ligands through reaction with D2O. This activity is attributed to the presence of the nanoparticles rather than to the presence of the oxidized palladium/DMAP complexes.
Flanagan
Keith A
KA
School of Chemistry and Chemical Biology, University College Dublin, Belfield, Dublin 4, Ireland.
Sullivan
James A
JA
Müeller-Bunz
Helge
H
D015761:4-Aminopyridine / Q000031:analogs & derivatives* / Q000737:chemistry; D018360:Crystallography, X-Ray; D003903:Deuterium / Q000737:chemistry; D017666:Deuterium Oxide / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D008958:Models, Molecular; D015394:Molecular Structure; D053758:Nanoparticles / Q000737:chemistry*; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry*; D010165:Palladium / Q000737:chemistry*; D010316:Particle Size; D013499:Surface Properties
D009942:Organometallic Compounds; D010165:Palladium; D006859:Hydrogen; D003903:Deuterium; D015761:4-Aminopyridine; D017666:Deuterium Oxide; C003885:4-dimethylaminopyridine