A P−H Functionalized Al/P Frustrated Lewis Pair: Substrate Activation and Selective Hydrogen Transfer

Hydroalumination of an alkynylphosphine gave an unprecedented P−H functionalized frustrated Lewis pair (FLP). The reactive P−H group does not influence the typical FLP properties, but the activation of substrates follows a new reaction pattern involving hydrogen transfer to yield unusual compounds with phosphaurea, iminophosphine, or phosphanyltriazene structural motifs. Cooperative activation and hydrogen shift is observed as a new reactivity pattern upon treatment of a P−H functionalized Al/P frustrated Lewis pair with various unsaturated substrates. Unusual highly functionalized phosphorus compounds were obtained, such as a phosphinyltriazene or phosphaurea. With benzonitrile, the sequence adduct formation, activation, and H‐shift gives an iminophosphine (see scheme).