Dinitrogen Splitting Coupled to Protonation |
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Authors: | Dr. Gleb A. Silantyev Moritz Förster Bastian Schluschaß Josh Abbenseth Dr. Christian Würtele Christian Volkmann Prof. Dr. Max C. Holthausen Prof. Dr. Sven Schneider |
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Affiliation: | 1. Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077 Göttingen, Germany;2. Insitut für Anorganische und Analytische Chemie, Goethe-Universität, Max-von-Laue-Strasse 7, 60438 Frankfurt am Main, Germany |
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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. |
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Keywords: | Distickstoff Molybdän Pincer-Liganden Protonierung Stickstoff-Fixierung |
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