Modulating Hydrogen Shuttling in Ammonia by Neutral and Cationic Boron‐Containing Frustrated Lewis Pairs (FLPs)

Abstract Xanthene‐backbone FLPs featuring secondary borane functions −B(Ar X )H (where Ar X =C 6 F 5 (Ar F ) or C 6 Cl 5 (Ar Cl )) have been targeted through reactions of the dihydroboranes Me 2 S ⋅ BAr X H 2 with [4,5‐xanth(PR 2 )Li] 2 (R=Ph, i Pr), and investigated in the synthesis of related cationic systems via hydride abstraction. The reactivity of these systems (both cationic and charge neutral) with ammonia have been probed, with a view to probing the potential for proton shuttling via N−H bond ‘activation.’ We find that in the case of four‐coordinate boron systems (cationic or change neutral), the N−H linkage remains intact, supported by a NH⋅⋅⋅P hydrogen bond which is worth up to 17 kcal mol −1 thermodynamically, and enabled by planarization of the flexible xanthene scaffold. For cationic three coordinate systems, N‐to‐P proton transfer is viable, driven by the ability of the boron centre to stabilise the [NH 2 ] − conjugate base through N‐to‐B π bonding. This proton transfer can be shown to be reversible in the presence of excess ammonia, depending on the nature of the B‐bound Ar X group. It is viable in the case of C 6 F 5 substituents, but is prevented by the more sterically encumbering and secondary donor‐stabilising capabilities of the C 6 Cl 5 substituent.