Computational Study of the Donor-Acceptor Interactions Underlying the Variable Oxygen Probe

Abstract

The variable oxygen probe (VOP) is a crystallographic technique that has been used to explore the relative donor abilities of various filled orbitals ranging from vicinal lone pairs to polarized heteroatom-carbon bonds, remote π functionalities, and strained carbon-carbon (CC) bonds. In this study, the donor-acceptor interactions which underlie the VOP have been explored in the gas phase using density functional theory on the model systems 1-13 with natural bond orbital analysis of the various donor-acceptor interactions involving both neutral and charged σ* antibonding orbitals as the acceptor probes. Updated values for the VOP slopes of 1-13 were shown to relate qualitatively with the sum ..