Dinitrogen Splitting Coupled to Protonation. Issue 21 (24th April 2017)

• Record Type: Journal Article
• Authors: Silantyev, Gleb A.; Förster, Moritz; Schluschaß, Bastian; Abbenseth, Josh; Würtele, Christian; Volkmann, Christian; Holthausen, Max C.; Schneider, Sven
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 21(2017)
• Page Start: 5872
• Page End: 5876
• Publication Date: 2017-04-24
• Subjects: dinitrogen -- molybdenum -- nitrogen fixation -- pincer ligand -- protonation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201701504
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The coupling of electron‐ and proton‐transfer steps provides a general concept to control the driving force of redox reactions. N2 splitting of a molybdenum dinitrogen complex into nitrides coupled to a reaction with Brønsted acid is reported. Remarkably, our spectroscopic, kinetic, and computational mechanistic analysis attributes N−N bond cleavage to protonation in the periphery of an amide pincer ligands rather than the {Mo−N2 −Mo} core. The strong effect on electronic structure and ultimately the thermochemistry and kinetic barrier of N−N bond cleavage is an unusual case of a proton‐coupled metal‐to‐ligand charge transfer process, highlighting the use of proton‐responsive ligands for nitrogen fixation. Abstract : Acid splits : Protonation of an N2 ‐bridged dimolybdenum complex in the pincer periphery results in splitting into Mo V nitrides. This proton‐coupled metal‐to‐ligand charge transfer reaction provides a mechanism to control the thermochemistry and kinetics of N−N bond cleavage with proton‐responsive ligands.