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Investigation of Lewis Acid-Carbonyl Solution Interactions via Infrared-Monitored Titration.

ABSTRACT: Lewis acid-activation of carbonyl-containing substrates is broadly utilized in organic synthesis. In order to facilitate the development of novel reaction pathways and understand existing methods, it is necessary to determine the solution interactions between Lewis acids and Lewis bases. Herein, we report the application of in situ infrared spectroscopy and solution conductivity toward the identification of the solution structures formed when a range of carbonyl compounds are combined with catalytically active metal halide Lewis acids under synthetically relevant conditions. These data are consistent with formation of Lewis acid-dependent complexes, where metals of low relative Lewis acidity display no ground state interaction with carbonyls. Conversely, we observed the formation of polyligated complexes when stronger Lewis acids (SnCl4, TiCl4, ZrCl4, FeCl3, and AlCl3) were treated with ketones, aldehydes, and esters. This collection of observations is intended to assist the synthetic chemist in the design of new catalysts and the development of novel methods.

SUBMITTER: Hanson CS

PROVIDER: S-EPMC7223869 | biostudies-literature | 2020 Jan

REPOSITORIES: biostudies-literature

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Investigation of Lewis Acid-Carbonyl Solution Interactions via Infrared-Monitored Titration.

Hanson Carly S CS Psaltakis Mary C MC Cortes Janiel J JJ Siddiqi Sameera S SS Devery James J JJ

The Journal of organic chemistry 20191227 2

Lewis acid-activation of carbonyl-containing substrates is broadly utilized in organic synthesis. In order to facilitate the development of novel reaction pathways and understand existing methods, it is necessary to determine the solution interactions between Lewis acids and Lewis bases. Herein, we report the application of in situ infrared spectroscopy and solution conductivity toward the identification of the solution structures formed when a range of carbonyl compounds are combined with catal ...[more]

PMID: 31830419

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Project description:The high sensitivity of silole- and silafluorene-containing polymers for detecting organic nitro, nitrate, and nitramine explosives cannot be solely attributed to favorable analyte-polymer hydrophobic interactions and amplified fluorescence quenching due to delocalization along the polymer chain. The Lewis acidity of silicon in conjugated poly(silafluorene-vinylene)s is shown to be important. This was established by examining the (29)Si NMR chemical shifts (Delta) for the model trimer fragment of the polymer CH(3)-silafluorene-(trans-C(2)H(2))-silafluorene-(trans-C(2)H(2))-silafluorene-CH(3). The peripheral and central silicon resonances are up-field from a TMS reference at -9.50 and -18.9 ppm, respectively. Both resonances shift down-field in the presence of donor analytes and the observed shifts (0 to 1 ppm) correlate with the basicity of a variety of added Lewis bases, including TNT. The most basic analyte studied was acetonitrile and an association constant (K(a)) of 0.12 M(-1) was calculated its binding to the peripheral silicon centers using the Scatchard method. Spin-lattice relaxation times (T(1)) of 5.86(3) and 4.83(4) s were measured for the methyl protons of acetonitrile in benzene-d(6) at 20 degrees C in the absence and presence of the silafluorene trimer, respectively. The significant change in T(1) values further supports a binding event between acetonitrile and the silafluorene trimer. These studies as well as significant changes and shifts observed in the characteristic UV-Vis absorption of the silafluorene group support an important role for the Lewis acid character of Si in polymer sensors that incorporate strained silacycles. The nitro groups of high explosives may act as weak Lewis-base donors to silacycles. This provides a donor-acceptor interaction that may be crucial for orienting the explosive analyte in the polymer film to provide an efficient pathway for inner-sphere electron transfer during the electron-transfer quenching process.

Dataset Information

Investigation of Lewis Acid-Carbonyl Solution Interactions via Infrared-Monitored Titration.

Publications

Investigation of Lewis Acid-Carbonyl Solution Interactions via Infrared-Monitored Titration.

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