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On the Use of Aqueous Metal-Aqua pKa Values as a Descriptor of Lewis Acidity
preprintsubmitted on 13.10.2020, 22:45 and posted on 14.10.2020, 13:14 by Amit Kumar, James Blakemore
The behavior of Lewis acidic metal ions in multimetallic systems has become a subject of intense interest in recent years. Parametrizing the behavior of these ions in non-aqueous conditions, commonly used in the field, is challenging due to the lack of direct measures of the Lewis acidity of metal ions in polar organic solvents. Here, we report the use of triphenylphosphine oxide (TPPO) as a 31P nuclear magnetic resonance (NMR) probe to quantify the Lewis acidity of a library of metal triflate salts using the Gutmann-Beckett method. A plot of the pKa values of the corresponding metal-aqua species, [M(H2O)m]n+, measured in H2O, vs. the 31P NMR shifts of TPPO in the presence of these metals in deuterated acetonitrile (d3-MeCN) and deuterated dichloromethane (CD2Cl2) displays a tightly co-linear relationship, suggesting similar behavior for these ions in water, d3-MeCN, and CD2Cl2. This collinearity reinforces the utility of the common approach of using the aqueous pKa values as a descriptor of Lewis acidity, regardless of the solvent used in the immediate experiments, and provides an insight into the usefulness of this descriptor in wide-ranging applications. Titration studies in d3-MeCNsuggest 1:1 binding of TPPO with monovalent ions, greater than 1:1 binding with divalent ions, and formation of multiple species with the highly Lewis acidic trivalent ions. Together, these data suggest that both aqueous pKa values and other single-measurement descriptors, while useful, provide only a snapshot of the influence of Lewis acidity on multimetallic chemical systems.
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