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Published on: May 6, 2020
Kinetic effects in heterometallic dinitrogen cleavage
1Department of Chemistry and Biochemistry, 251 Nieuwland Science Hall, University of Notre Dame, Notre Dame, Indiana 46556-5670, USA.
The reaction of a rhenium dinitrogen complex with a molybdenum complex forms a bridged dinitrogen species. This complex is stable, indicating kinetic, not thermodynamic, control over nitrogen cleavage and nitride coupling for nitrogen fixation strategies.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Nitrogen Fixation Research
Background:
- Dinitrogen (N2) is a highly stable molecule, making its cleavage and conversion into useful nitrogen compounds challenging.
- Understanding the reactivity of metal-dinitrogen complexes is crucial for developing catalytic nitrogen fixation processes.
- Previous studies have explored various metal complexes for N2 activation and transformation.
Purpose of the Study:
- To synthesize and characterize a novel N(2)-bridged rhenium-molybdenum complex.
- To investigate the stability and reactivity of the bridging dinitrogen moiety.
- To explore the implications of these findings for nitrogen fixation strategies.
Main Methods:
- Synthesis of the rhenium(I) dinitrogen complex (PhMe2P)4ClRe(N2).
- Reaction with [Mo2(S2CNEt2)6](OTf)2 to form the bridged complex [(PhMe2P)4ClRe(mu-N2)Mo(S2CNEt2)3]OTf.
- Characterization using spectroscopic (IR) and X-ray crystallographic methods.
Main Results:
- Formation of the N(2)-bridged complex [7]OTf was confirmed.
- Spectroscopic and structural data indicated slight activation of the bridging N2 moiety but overall stability against cleavage.
- The putative nitride products, (Et2NCS2)3Mo(N) and [(PhMe2P)(4)ClRe(N)]OTf, were stable and did not couple.
Conclusions:
- The stability of the bridged dinitrogen complex is governed by kinetic factors, not thermodynamic stability of the N-N bond.
- The observed inertness disfavors N2 cleavage and nitride coupling, posing challenges for certain nitrogen fixation pathways.
- These findings provide insights into the limitations of using polar effects to facilitate N2 cleavage for nitrogen fixation.
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