Ammonia activation using a heteroleptic stannylene and lithium stannylenoid formation facilitated by hemilabile iminophosphorane-based ligands

Heteroleptic stannylenes, featuring pendant hemilabile iminophosphorane functionalities and kinetically stabilizing terphenyl ligands, were synthesized straightforwardly through formal C-H activation. Subsequently, they were investigated for their ability to activate ammonia through N-H bond scission. By combining synthetic modifications of the ancillary ligand framework and computational analyses, detailed insights into the mechanism of NH 3 activation by these systems were obtained, highlighting an activation pathway at tin without a change in oxidation state. Additionally, an observed by-product during these studies underscores the non-innocence of a lithium salt in the synthesis of the stannylene starting materials, providing access to a novel lithium stannylenoid. Heteroleptic stannylenes with iminophosphorane and terphenyl ligands were synthesized and studied for NH 3 activation. Synthetic and computational analyses revealed a redox-neutral activation path and identified a novel lithium stannylenoid byproduct.