This talk, which honors the academic career of Professor Arnie Rheingold over the past half-century for his leadership role in promoting the use of X-ray diffraction to inorganic chemists as a routine analytical tool, will primarily focus upon our recent/current research on the preparation and crystallographic/spectroscopic characterization of CO/PR3-ligated heterometallic palladium clusters.Experimental evidence will be given indicating that the so-called �inert� 6s2 electron-pair of 6s25d10 Tl(I) can exert either a positive or negative stabilizing influence relative to that of corresponding 6s05d10 Au(I) in different bimetallic closed-shell Tl-M clusters (M = Pd, Pt).Compelling experimental/theoretical implications will also be presented that the observed CO stabilities of the bimetallic Au2Pd21 and Au2Pd28 clusters (relative to nanosized homopalladium Pdn clusters with n>10 being generally unstable under CO) is a consequence in both neutral Au-Pd clusters of electron delocalization over the entire cluster of each Au 6s valence electron toward a Au+ configuration. This important finding is directly linked to a recent report on Au-Pd nanoparticle catalysts used for the complete conversion of formic acid to high-quality hydrogen (and CO2) that the presence of Au prevents CO poisoning.This talk will also include brief comments concerning my long-held prejudices in the teaching of modern chemical crystallography, especially on point group and space group symmetry.

Extraordinary structure/bonding and chemical reactivity consequences upon incorporation of gold, thallium, or platinum into nanosized CO/PR<sub>3</sub>-ligated homopalladium clusters

243rd National Meeting (2012)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Extraordinary structure/bonding and chemical reactivity consequences upon incorporation of gold, thallium, or platinum into nanosized CO/PR3-ligated homopalladium clusters

Extraordinary structure/bonding and chemical reactivity consequences upon incorporation of gold, thallium, or platinum into nanosized CO/PR₃-ligated homopalladium clusters