Beyond Steric Crowding: Dispersion Energy Donor Effects in Large Hydrocarbon Ligands.

Abstract

Interactions between sterically crowded hydrocarbon-substituted ligands are widely considered to be repulsive because of the intrusion of the electron clouds of the ligand atoms into each other's space, which results in Pauli repulsion. Nonetheless, there is another interaction between the ligands which is less widely publicized but is always present. This is the London dispersion (LD) interaction which can occur between atoms or molecules in which dipoles can be induced instantaneously, for example, between the H atoms from the ligand C-H groups.These LD interactions are always attractive, but their effects are not as widely recognized as those of the Pauli repulsion despite their central role in the formation of condensed matter. Their relatively poor recognition is probably due to the relative weakness (ca. 1 kcal mol-1) of individual H···H interactions owing to their especially strong distance dependence. In contrast, where there are numerous H···H interactions, a collective LD energy equaling several tens of kcal mol-1 may ensue. As a result, in some molecules the latent importance of the LD attraction energies emerges and assumes a prominence that can overshadow the Pauli effects (e.g., in the stabilization of high-oxidation-state transition-metal alkyls, inducing disproportionation reactions, or in the stabilization of otherwise unstable bonds).Despite being known for over a century, the accurate quantification of individual H···H LD effects in molecular species is a relatively recent phenomenon and at present is based mainly on modified DFT calculations. A few leading reviews summarized these earlier studies of the C-H···H-C LD interactions in organic molecules, and their effects on the structures and stabilities were described. LD effects in sterically crowded inorganic and organometallic molecules have been recognized.The author's interest in these LD effects arose fortuitously over a decade ago during research on sterically crowded heavier main-group element carbene analogues and two-coordinate, open-shell (d1-d9) transition-metal complexes where counterintuitive steric effects were observed. More detailed explanations of these effects were provided by dispersion-corrected DFT calculations in collaboration with the groups of Tuononen and Nagase (see below).This Account describes our development of these initial results for other inorganic molecular classes. More recently, the work has led us to move to the planned inclusion of dispersion effects in ligands to stabilize new molecular types with theoretical input from the groups of Vasko and Grimme (see below). Our approach sought to use what Grimme has described as dispersion effect donor (DED) groups (i.e., spatially close-lying, densely packed substituents either as ligands (e.g., -C6H2-2,4,6-Cy3, Cy = cyclohexyl) or as parts of ligands (e.g., a Cy substituent) that produce relatively large dispersion energies to stabilize these new compounds.We predict that the future design of sterically crowding hydrocarbon ligands will include the consideration and incorporation of LD effects as a standard methodology for directed use in the attainment of new synthetic targets.