Experimental Quantum Chemistry: A Hammett-inspired Fingerprinting of Substituent Effects.

ABSTRACT: The quantum mechanically calculable Q descriptor is shown to be a potent quantifier of chemical reactivity in complex molecules - it shows a strong correlation to experimentally derived field effects in non-aromatic substrates and Hammett σ_m and σ_p parameters. Models for predicting substituent effects from Q are presented and applied, including on the elusive pentazolyl substituent. The presented approach enables fast computational estimation of substituent effects, and, in extension, medium-throughput screening of molecules and compound design. An experimental dataset is suggested as a candidate benchmark for aiding the general development and comparison of electronic structure analyses. It is here used to evaluate the experimental quantum chemistry (EQC) framework f

SUBMITTER: Sessa F 

PROVIDER: S-EPMC8049055 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature