Issue 10, 2021

Mechanistic elucidation of monoalkyltin(iv)-catalyzed esterification

Abstract

Monoalkyltin(IV) complexes are well-known catalysts for esterification reactions and polyester formation, yet the mode of operation of these Lewis acidic complexes is still unknown. Here, we report on mechanistic studies of n-butylstannoic acid in stoichiometric and catalytic reactions, analyzed by NMR, IR and MS techniques. While the chemistry of n-butyltin(IV) carboxylates is dominated by formation of multinuclear tin assemblies, we found that under catalytically relevant conditions only monomeric n-BuSn(OAc)3 and dimeric (n-BuSnOAc2OEt)2 are present. Density functional theory (DFT) calculations provide support for a mononuclear mechanism, where n-BuSn(OAc)3 and dimeric (n-BuSnOAc2OEt)2 are regarded as off-cycle species, and suggest that carbon–oxygen bond breaking is the rate-determining step.

Graphical abstract: Mechanistic elucidation of monoalkyltin(iv)-catalyzed esterification

Supplementary files

Article information

Article type
Paper
Submitted
01 Feb 2021
Accepted
17 Feb 2021
First published
17 Feb 2021
This article is Open Access
Creative Commons BY-NC license

Catal. Sci. Technol., 2021,11, 3326-3332

Mechanistic elucidation of monoalkyltin(IV)-catalyzed esterification

L. A. Wolzak, J. J. Hermans, F. de Vries, K. J. van den Berg, J. N. H. Reek, M. Tromp and T. J. Korstanje, Catal. Sci. Technol., 2021, 11, 3326 DOI: 10.1039/D1CY00184A

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