0000000000861697
AUTHOR
Warren Piers
Mechanistic Studies on the Metal-Free Activation of Dihydrogen by Antiaromatic Pentarylboroles
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 suppo…
Direct observation of a borane–silane complex involved in frustrated Lewis-pair-mediated hydrosilylations
Perfluorarylborane Lewis acids catalyse the addition of silicon–hydrogen bonds across C=C, C=N and C=O double bonds. This ‘metal-free’ hydrosilylation has been proposed to occur via borane activation of the silane Si–H bond, rather than through classical Lewis acid/base adducts with the substrate. However, the key borane/silane adduct had not been observed experimentally. Here it is shown that the strongly Lewis acidic, antiaromatic 1,2,3-tris(pentafluorophenyl)-4,5,6,7-tetrafluoro-1-boraindene forms an observable, isolable adduct with triethylsilane. The equilibrium for adduct formation was studied quantitatively through variable-temperature NMR spectroscopic investigations. The interacti…
Dihydrogen Activation by Antiaromatic Pentaarylboroles
Facile metal-free splitting of molecular hydrogen (H2) is crucial for the utilization of H2 without the need for toxic transition-metal-based catalysts. Frustrated Lewis pairs (FLPs) are a new class of hydrogen activators wherein interactions with both a Lewis acid and a Lewis base heterolytically disrupt the hydrogen−hydrogen bond. Here we describe the activation of hydrogen exclusively by a boron-based Lewis acid, perfluoropentaphenylborole. This antiaromatic compound reacts extremely rapidly with H2 in both solution and the solid state to yield boracyclopent-3-ene products resulting from addition of hydrogen atoms to the carbons α to boron in the starting borole. The disruption of antiar…