By employing strongly σ-donating boryl ancillary ligands, the oxidative addition of H₂ to a single site Sn^II system has been achieved for the first time, generating (boryl)₂SnH₂. Similar chemistry can also be achieved for protic and hydridic E-H bonds (N-H/O-H, Si-H/B-H, respectively). In the case of ammonia (and water, albeit more slowly), E-H oxidative addition can be shown to be followed by reductive elimination to give an N- (or O-) borylated product. Thus, in stoichiometric fashion, redox-based bond cleavage/formation is demonstrated for a single Main Group metal center at room temperature. From a mechanistic viewpoint, a two-step coordination/proton transfer process for N-H activation is shown to be viable through the isolation of species of the types Sn(boryl)₂.NH₃ and [Sn(boryl)₂(NH₂)]^- and their onward conversion to the formal oxidative addition product Sn(boryl)₂(H)(NH₂).

A series of single component FLPs has been investigated for small molecule capture, with the finding that through tuning of both the thermodynamics of binding/activation and the degree of preorganization (i.e., ΔS^⧧) reversibility can be brought about at (or close to) room temperature. Thus, the dimethylxanthene system {(C₆H₄)₂(O)CMe₂}(PMes₂)(B(C₆F₅)₂): (i) heterolytically cleaves dihydrogen to give an equilibrium mixture of FLP and H₂ activation product in solution at room temperature and (ii) reversibly captures nitrous oxide (uptake at room temperature, 1 atm; release at 323 K).

The catalytic dehydrogenation of ammonia- and amine-boranes by a dimethylxanthene-derived frustrated Lewis pair (FLP) is described. Turnover is facilitated on a thermodynamic basis by the ready release of H₂ from the weakly basic PPh₂-containing system. In situ NMR studies and the isolation of intermediates from stoichiometric reactions provide evidence for a mechanism initiated by B-H activation, followed by end-growth BN coupling involving the terminal NH bond of the bound BN fragment and a BH bond of the incoming borane monomer.