5 years ago

Dinitrogen Splitting Coupled to Protonation

Dinitrogen Splitting Coupled to Protonation
Christian Würtele, Sven Schneider, Max C. Holthausen, Bastian Schluschaß, Gleb A. Silantyev, Moritz Förster, Josh Abbenseth, Christian Volkmann
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. Acid splits: Protonation of an N2-bridged dimolybdenum complex in the pincer periphery results in splitting into MoV 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.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/anie.201701504

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