What Distinguishes the Strength and the Effect of a Lewis Acid: Analysis of the Gutmann–Beckett Method

• Published in: Angewandte Chemie International Edition Vol. 61; no. 4; pp. e202114550 - n/a
• Main Authors: Erdmann, Philipp, Greb, Lutz
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 21.01.2022; John Wiley and Sons Inc
• Edition: International ed. in English
• Subjects: Acidity; computational Lewis acidity; deformation energy; Fluorides; Gutmann–Beckett; Lewis acid; Lewis acidity scale; Lewis acids; NMR; Nuclear magnetic resonance; Pair bond; Lewis acids; Gutmann-Beckett; computational Lewis acidity; Lewis acidity scale; deformation energy
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202114550

IUPAC defines Lewis acidity as the thermodynamic tendency for Lewis pair formation. This strength property was recently specified as global Lewis acidity (gLA), and is gauged for example by the fluoride ion affinity. Experimentally, Lewis acidity is usually evaluated by the effect on a bound molecule, such as the induced 31P NMR shift of triethylphosphine oxide in the Gutmann–Beckett (GB) method. This type of scaling was called effective Lewis acidity (eLA). Unfortunately, gLA and eLA often correlate poorly, but a reason for this is unknown. Hence, the strength and the effect of a Lewis acid are two distinct properties, but they are often granted interchangeably. The present work analyzes thermodynamic, NMR specific, and London dispersion effects on GB numbers for 130 Lewis acids by theory and experiment. The deformation energy of a Lewis acid is identified as the prime cause for the critical deviation between gLA and eLA but its correction allows a unification for the first time. What is the Gutmann–Beckett number? An experimental and theoretical evaluation of factors that determine the 31P NMR shifts of binding of 130 Lewis acids to triethylphosphine oxide allows linking the strength of a Lewis acid (global Lewis acidity) with the effect of a Lewis acid (effective Lewis acidity).