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Coffinet, Anaïs; Specklin, David; Vendier, Laure; Etienne, Michel; Simonneau, Antoine
Chemistry : a European journal, 2019-Nov-13, 2019-11-13, Letnik: 25, Številka: 63Journal Article
The first example of a formal 1,3-B-H bond addition across the M-N≡N unit of an end-on dinitrogen complex has been achieved. The use of Piers' borane HB(C F ) was essential to observe this reactivity and it plays a triple role in this transformation: 1) electrophilic N -borylation agent, 2) Lewis acid in a frustrated Lewis pair-type B-H bond activation, and 3) hydride shuttle to the metal center. This chemistry is supported by NMR spectroscopy and solid-state characterization of products and intermediates. The combination of chelate effect and strong σ donation in the diphosphine ligand 1,2-bis(diethylphosphino)ethane was mandatory to avoid phosphine dissociation that otherwise led to complexes where borylation of N occurred without hydride transfer.
