Gutmann-Beckett-type measurements with phosphine oxide probes can be used to estimate effective Lewis acidity with ³¹P nuclear magnetic resonance spectroscopy, but the influence of the molecular structure of a given probe on the quantification of Lewis acidity remains poorly documented in experimental work. Here, a quantitative comparison of triethyl (E), trioctyl (O), and triphenyl (P) phosphine oxides as molecular probes of Lewis acidity has been carried out via titration studies in MeCN with a test set of six mono- and divalent metal triflate salts. In comparison to E, the bulkier O displays a similar range of chemical shift values and binding affinities for the various test metal ions. Spectral linewidths and speciation properties vary for individual cation-to-probe ratios, however, confirming probe-specific properties that can impact the data quality. Importantly, P displays a consistently narrower dynamic range than both E and O, illustrating how electronic changes at phosphorus can influence the NMR response. Comparative parametrizations of the effective Lewis acidities of a broader range of metal ions, including the trivalent rare earth ions Y³⁺, Lu³⁺, and Sc³⁺ as well as the uranyl ion (UO₂²⁺), can be understood in light of these results, providing insight into the fundamental chemical processes underlying the useful approach of single-point measurements for quantification of effective Lewis acidity. Together with a study of counteranion effects reported here, these data clarify the diverse ensemble of factors that can influence the measurement of Lewis acid/base interactions.

Cecilia J. Paranjothi

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