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Updated: Apr 30, 2026
10:52
Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
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Dinitrogen splitting and functionalization in the coordination sphere of rhenium
Isabel Klopsch1, Markus Finger, Christian Würtele
1Institut für Anorganische Chemie, Georg-August-Universität , Tammannstraße 4, 37077 Göttingen, Germany.
Journal of the American Chemical Society
|May 1, 2014
Summary
Researchers synthesized a novel rhenium(III) complex that cleaves dinitrogen (N2) upon reduction. This process yields a unique rhenium(V) nitride, marking a first in rhenium coordination chemistry and enabling subsequent C-N bond formation.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Coordination Chemistry
Background:
- Rhenium complexes are explored for catalytic applications.
- Nitrogen fixation remains a significant challenge in chemistry.
- Pincer ligands offer unique coordination environments.
Purpose of the Study:
- To synthesize a novel rhenium(III) complex with a pincer ligand.
- To investigate the reactivity of the rhenium complex towards dinitrogen (N2) cleavage.
- To demonstrate the functionalization of a nitride ligand derived from N2.
Main Methods:
- Reaction of [ReCl3(PPh3)2(NCMe)] with the pincer ligand HN(CH2CH2PtBu2)2 (HPNP).
- Reduction of the resulting rhenium(III) complex to cleave N2.
- Characterization of the rhenium(V) nitride complex.
- Functionalization of the nitride ligand using MeOTf.
Main Results:
- Formation of the five-coordinate rhenium(III) complex [ReCl2(PNP)].
- Cleavage of N2 upon reduction to yield the rhenium(V) nitride complex [Re(N)Cl(PNP)], the first such example for rhenium.
- Demonstration of selective C-N bond formation on the nitride ligand.
Conclusions:
- A new pathway for N2 activation and functionalization using rhenium has been established.
- The synthesized rhenium(V) nitride complex is a key intermediate for nitrogen-based transformations.
- This work opens avenues for developing new catalytic processes involving nitrogen.
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