Reversible Heterolytic Si–H Bond Activation by an Intramolecular Frustrated Lewis Pair

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Abstract
The intramolecular frustrated P/B Lewis pair Mes2PCH2CH2B(C6F5)2 (7) reacts readily with phenylsilane by heterolytic cleavage of the Si-H bond to give the zwitterion [Mes2(PhH2Si)P+CH2CH2B-H(C6F5)2] (8a), which has been fully characterized and its structure confirmed by X-ray crystal structure analysis. Variable-temperature NMR studies revealed that the reaction is reversible. Adduct 8a is the predominant species (ca. 98%) in CD2Cl2 solution at low temperature (193 K), whereas at ambient temperature (299 K) it exists in a ca. 7 : 3 equilibrium with unreacted 7 and PhSiH3. Diphenylsilane reacted similarly with the frustrated Lewis pair 7, however, the equilibrium was found to favor the starting materials in the investigated temperature range.

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