Construction of frustrated Lewis pair from nitride and phosphine for the activation and cleavage of molecular hydrogen

Abstract

Activation and cleavage of molecular hydrogen (H2) to proton and hydride is an important task for several reasons, especially as a reagent in hydrogenation. In this scenario, with the support of density‐functional theory methods, a novel strategy has been devised for the conversion of coordinated nitride into ammonia using molecular hydrogen in the presence of tri‐tert‐butylphosphine (PtBu3). The proposed methodology is based on the formation of frustrated Lewis pair (FLP) from [OsVI(tpy)(Cl)2(N)]+ (tpy = 2,2′:6′,2′′‐terpyridine) and PtBu3 followed by reaction with molecular hydrogen to form an FLP–H2 adduct. The FLP–H2 adduct can further undergo H–H bond cleavage heterolytically to produce proton and hydride which can be eventually used for the functionalization of coordinated nitride to ammonia. The calculated energy profile comprising all possible intermediates and transition‐state molecules suggests that the proposed reaction pathway is energetically viable at elevated temperatures.