Examination of Protonation-Induced Dinitrogen Splitting by in Situ EXAFS Spectroscopy

Josh Abbenseth, Jean-Pierre H Oudsen, Bas Venderbosch, Serhiy Demeshko, Markus Finger, Christian Herwig, Christian Würtele, Max C Holthausen, Christian Limberg, Moniek Tromp*, Sven Schneider*

*Corresponding author for this work

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Abstract

The splitting of dinitrogen into nitride complexes emerged as a key reaction for nitrogen fixation strategies at ambient conditions. However, the impact of auxiliary ligands or accessible spin states on the thermodynamics and kinetics of N-N cleavage is yet to be examined in detail. We recently reported N-N bond splitting of a {Mo(μ2:η1:η1-N2)Mo}-complex upon protonation of the diphosphinoamide auxiliary ligands. The reactivity was associated with a low-spin to high-spin transition that was induced by the protonation reaction in the coordination periphery, mainly based on computational results. Here, this proposal is evaluated by an XAS study of a series of linearly N2 bridged Mo pincer complexes. Structural characterization of the transient protonation product by EXAFS spectroscopy confirms the proposed spin transition prior to N-N bond cleavage.

Original languageEnglish
Pages (from-to)14367-14375
Number of pages9
JournalInorganic Chemistry
Volume59
Issue number19
DOIs
Publication statusPublished - 2020

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