Thermoneutral N−H Bond Activation of Ammonia by a Geometrically Constrained Phosphine
Josh Abbenseth, Oliver P. E. Townrow, José M. Goicoechea
Abstract
Abstract A geometrically constrained phosphine bearing a tridentate NNS pincer ligand is reported. The effect of the geometric constraint on the electronic structure was probed by theoretical calculations and derivatization reactions. Reactions with N−H bonds result in formation of cooperative addition products. The thermochemistry of these transformations is strongly dependent on the substrate, with ammonia activation being thermoneutral. This represents the first example of a molecular compound that reversibly activates ammonia via N−H bond scission in solution upon mild heating.
Topics & Concepts
PhosphineThermochemistryChemistryAmmoniaLigand (biochemistry)Bond cleavageSubstrate (aquarium)Computational chemistryPhotochemistryInorganic chemistryOrganic chemistryCatalysisOceanographyBiochemistryReceptorGeologyAsymmetric Hydrogenation and CatalysisCatalytic Cross-Coupling ReactionsOrganometallic Complex Synthesis and Catalysis