Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles
Houghton, A., Karttunen, V., Fan, C., Piers, W., & Tuononen, H. (2013). Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles. Journal of the American Chemical Society, 135 (2), 941-947. doi:10.1021/ja311842r
Published inJournal of the American Chemical Society
DisciplineEpäorgaaninen ja analyyttinen kemia
© 2012 American Chemical Society. This is a final draft version of an article whose final and definitive form has been published by ACS. Published in this repository with the kind permission of the publisher.
The perfluoro- and perprotiopentaphenylboroles 1 and 2 react with dihydrogen to effect H–H bond cleavage and formation of boracyclopentene products. The mechanism of this reaction has been studied experimentally through evaluation of the kinetic properties of the slower reaction between 2 and H2. The reaction is first-order in both [borole] and [H2] with activation parameters of ΔH⧧ = 34(8) kJ/mol and ΔS⧧ = −146(25) J mol–1 K–1. A minimal kinetic isotope effect of 1.10(5) was observed, suggesting an asynchronous geometry for H–H cleavage in the rate-limiting transition state. To explain the stereochemistry of the observed products, a ring-opening/ring-closing mechanism is proposed and supported by the separate synthesis of a proposed intermediate and its observed conversion to product. Furthermore, extensive DFT mapping of the reaction mechanism supports the plausibility of this proposal. The study illustrates a new mechanism for the activation of H2 by a strong main group Lewis acid in the absence of an external base, a process driven in part by the antiaromaticity of the borole rings in 1 and 2. ...