A (bisborane)triarylphosphine was developed to spontaneously generate H2 from water under ambient conditions, revealing an unprecedented multi-centered electron relay mechanism for a metal-free umpolung of proton to hydride.

A new efficient metal-based frustrated Lewis pair constructed by (P t Bu 3) 2 Pt and B(C 6 F 5) 3 was designed through density functional theory calculations for the catalytic dehydrogenation of ammonia borane (AB). The reaction was composed by the successive dehydrogenation of AB and H 2 liberation, which occurs through the cooperative functions of the Pt(0) center and the B(C 6 F 5) 3 moiety. Two equivalents of H 2 were predicted to be liberated from each AB molecule. The generation of the second H2 is the rate-determining step, with a Gibbs energy barrier and reaction energy of 27.4 and 12.8 kcal/mol, respectively.