Calorimetric Study of the Activation of Hydrogen by Tris(pentafluorophenyl)borane and Trimesitylphosphine.

The mechanism of H2 heterolysis by the frustrated Lewis pair of B(C6F5)3 and P(mes)3 was investigated by isothermal reaction calorimetry in the temperature range from 30 to 90 °C. The experimental heat curves were modeled in Berkeley Madonna to obtain both kinetic and thermodynamics data simultaneously. The H2 activation reaction is treated as a single, termolecular step with a rate constant of 0.61 M-2 s-1 at 303 K with an exothermic enthalpy of reaction, ΔHH2 = -141 kJ/mol. An Eyring analysis gave activation parameters of ΔH‡ = 13.6(9) kJ mol-1 and ΔS‡ = -204(85) J K-1 mol-1. Using D2 gas in place of H2 gas provided an opportunity to measure the relative rates of D2 versus H2 heterolysis to yield a the kinetic isotope effect, KIE = 1.1(1).

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 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.

Hydrogen activation with perfluorinated organoboranes: 1,2,3-tris(pentafluorophenyl)-4,5,6,7-tetrafluoro-1-boraindene.

The perfluorinated boraindene was synthesized and fully characterized. Both computational and crystallographic data show that is antiaromatic. Compound was shown to react reversibly with H2 and to catalyse the hydrogenation of cyclohexene. The mechanism of catalysis was probed experimentally and computationally.

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 interaction of the silane with the borane occurs through the Si-H bond, as evidenced by trends in the Si-H coupling constant and the infrared stretching frequency of the Si-H bond, as well as by X-ray crystallography and theoretical calculations. The adduct's reactivity with nucleophiles demonstrates conclusively the role of this species in metal-free 'frustrated-Lewis-pair' hydrosilylation reactions.

Silane-controlled diastereoselectivity in the tris(pentafluorophenyl)borane-catalyzed reduction of alpha-diketones to silyl-protected 1,2-Diols.

B(C(6)F(5))(3)-catalyzed bis(hydrosilylation) of alpha-diketones can give high diastereomeric excess of either meso/anti (small silanes and disilane reagents) or dl/syn (bulky silanes) silyl-protected 1,2-diols. This easily tuned diastereoselectivity is rationalized based on the classic Felkin-Anh model applied to a mechanism relying on Si-H abstraction by the electrophilic borane reagent.