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Instruments / Technical Area	Publication Details	Published	Actions
B18-Core EXAFS	Examination of protonation-induced dinitrogen splitting by in situe XAFS 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 Inorganic Chemistry DOI: 10.1021/acs.inorgchem.0c02134 Diamond Proposal Number(s): [22432] Show Abstract ▼ 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.	Sep 2020

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