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Examination of protonation-induced dinitrogen splitting by in situe XAFS spectroscopy
DOI:
10.1021/acs.inorgchem.0c02134
Authors:
Josh
Abbenseth
(University of Göttingen)
,
Jean-pierre H.
Oudsen
(University of Amsterdam)
,
Bas
Venderbosch
(University of Amsterdam)
,
Serhiy
Demeshko
(Georg- August-Universitaẗ Göttingen)
,
Markus
Finger
(Georg- August-Universitaẗ Göttingen)
,
Christian
Herwig
(Humboldt Universitaẗ zu Berlin)
,
Christian
Würtele
(Humboldt Universitaẗ zu Berlin)
,
Max C.
Holthausen
(Goethe-Universitaẗ)
,
Christian
Limberg
(Humboldt Universitaẗ zu Berlin)
,
Moniek
Tromp
(University of Groningen)
,
Sven
Schneider
(Georg- August-Universitaẗ Göttingen)
Co-authored by industrial partner:
No
Type:
Journal Paper
Journal:
Inorganic Chemistry
State:
Published (Approved)
Published:
September 2020
Diamond Proposal Number(s):
22432
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.
Journal Keywords: Redox reactions; Reaction mechanisms; Extended X-ray absorption fine structure; Physical and chemical processes; Quantum mechanics
Subject Areas:
Chemistry
Instruments:
B18-Core EXAFS