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Thermoneutral N-H Bond Activation of Ammonia by a Geometrically Constrained Phosphine.

Josh AbbensethOliver P E TownrowJose M Goicoechea
Published in: Angewandte Chemie (International ed. in English) (2021)
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.
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