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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.

SUBMITTER: Wolzak LA

PROVIDER: S-EPMC8147323 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Mechanistic elucidation of monoalkyltin(iv)-catalyzed esterification.

Wolzak Lukas A LA Hermans Joen J JJ de Vries Folkert F van den Berg Keimpe J KJ Reek Joost N H JNH Tromp Moniek M Korstanje Ties J TJ

Catalysis science & technology 20210217 10

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 <i>n</i>-butylstannoic acid in stoichiometric and catalytic reactions, analyzed by NMR, IR and MS techniques. While the chemistry of <i>n</i>-butyltin(iv) carboxylates is dominated by formation of multinuclear tin assemblies, we found that under catalytically relevant conditi ...[more]

PMID: 34123363

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