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Mechanistic studies on the metal-free activation of dihydrogen by antiaromatic pentarylboroles.

Authors
Type
Published Article
Journal
Journal of the American Chemical Society
1520-5126
Publisher
American Chemical Society
Publication Date
Volume
135
Issue
2
Pages
941–947
Identifiers
DOI: 10.1021/ja311842r
PMID: 23259404
Source
Medline
License
Unknown

Abstract

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 H(2). The reaction is first-order in both [borole] and [H(2)] 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 H(2) 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.

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