Computational Design of Frustrated Lewis Pairs as a Strategy for Catalytic Hydrogen Activation and Hydrogenation Catalyst

[Image: see text] Catalytic hydrogenation is one of the most important reaction types commonly used in chemistry and chemical industry. Recently, there has been significant interest in developing a metal-free hydrogenation catalyst to avoid the problems caused by using heavy transition metal catalysts. On the basis of the advances of metal-free hydrogen activation with frustrated Lewis pairs (FLPs, e.g. tBu(3)P/B(C(6)F(5))(3)) which often uses boron as a Lewis acid center, we computationally explored the prospect for phosphorus(V) and sulfur(VI) as Lewis acid centers to construct FLPs for hydrogen activation and hydrogenation. We found out that the proposed FLPs with P(V)- or S(VI)-centered Lewis acid can also activate H(2) with a mechanism similar to that used by the conventional FLPs. A heterolytic cleavage of H–H is achieved when electrons are donated simultaneously from the σ orbital of H(2) to the empty orbital of the Lewis acid center and from the lone-pair orbital of the Lewis base center to the σ* orbital of H(2). The multiple C–H···F hydrogen bonds further aid the association of the pairs for H(2) activation. Some of our designed FLPs possess kinetics and thermodynamics for developing hydrogenation catalysts. This computational exploration could inspire experimental development of a new type of FLPs with P(V) or S(VI) or a Lewis acid partner for FLPs for reversible H(2) activation.