Large Solvent Isotope Effect Associated with the Hydrolysis of Allylindium Iodide.

Author(s) Koszinowski, K.; Stephenson, D.S.
Journal J Org Chem
Date Published 2018 Nov 09
Abstract

Allylindium halides are valuable allylating reagents, which can even be applied in aqueous solutions. Previous H NMR spectroscopic investigations suggested that these reagents are stable for several hours in DO, whereas ESI-mass spectrometric experiments in HO pointed to much shorter lifetimes. To resolve this seeming discrepancy, the present study systematically examines the solvolysis of allylindium iodide in HO, DO, and mixtures thereof by both analytical methods. Kinetic measurements find a large kinetic isotope effect (KIE = 12.0 ± 1.5 at 298 K), which fully explains the different behavior in HO and DO. Moreover, new intact and partially hydrolyzed allylindium intermediates are detected. Additional experiments on solutions of allylindium iodide in CHOH, CHOD, and EtOH observe ions identical or similar to those present in aqueous solutions, but determine a somewhat smaller kinetic isotope effect.

DOI 10.1021/acs.joc.8b01971
ISSN 1520-6904
Citation Koszinowski K, Stephenson DS. Large Solvent Isotope Effect Associated with the Hydrolysis of Allylindium Iodide. J Org Chem. 2018.

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