Hop-Skip-Jump: Monovalent Metals on the Surface of the Phenalenyl Radical

Abstract

The phenalenyl radical (P) and its relatively stable cation and anion are of interest for applications in areas spanning magnetic materials and ligand development for reaction catalysis. We report on a broad investigation of the bonding, thermochemistry, and kinetics of PM complexes where M is a group 1 or 11 metal atom. The PM species that are considered in this work afford a simplified picture of the behavior of metal adatoms on hydrogen terminated graphene fragments, and, more crucially, we expand a still nascent understanding of the organometallic chemistry of P. The exceptional fluxionality of group 1 metals on the phenalenyl surface is predicted, the associated energy barriers are quantified, and the major role of relativistic effects in restricting the fluxionality of Au on the surface is demonstrated. Although relativistic effects swell the barriers to isomerization, we find that orbital size and energies, even in the absence of relativistic effects, dictate different path preferences for the motion of Au on the surface of the radical compared to Cu and Ag.

Twenty years of exceptional success: The molecular education and research consortium in undergraduate computational chemistry (MERCURY)

“…Kelling Donald's research: In the Donald research group, work is focused on (a) halogen bonding and other sigma hole interactions in organic and inorganic systems, [ 210,278 ] (b) fluxionality in planar inorganic clusters and the nature and potential control of so‐called molecular machines, [ 208,263 ] (c) the evolution of structural preferences and thermal stability in metal halide and hydride molecules, clusters, and corresponding extended solids, [ 322 ] (d) the stability and catalytic applications of structurally interesting or unusual main‐group and transition‐metal organometallic compounds, [ 151,231,351,385 ] (e) the stabilization of unusual bonding arrangements, including planar tetra‐coordinate and other unusual coordination environments, [ 172 ] (f) quantifying currently qualitative but transferrable concepts in chemical bonding, [ 233 ] and (g) aromaticity and analogous phenomena in non‐hydrocarbon systems. [ 338,386 ] The MRI resources are essential for calculations on large and heavy elemental systems.…”