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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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Oxidative Coupling of Terminal Rhenium Pnictide Complexes
Josh Abbenseth1, Martin Diefenbach2, Alexander Hinz3
1Georg-August-Universität, Institut für Anorganische Chemie, Tammannstraße 4, 37077, Göttingen, Germany.
Angewandte Chemie (International Ed. in English)
|June 11, 2019
Summary
Researchers isolated novel rhenium(V) complexes featuring terminal phosphide and arsenide ligands. These complexes undergo Pn-Pn coupling upon oxidation, forming unique {Pn2}0 species stabilized by metal and pyrazole interactions.
Area of Science:
- Inorganic Chemistry
- Organometallic Chemistry
- Materials Science
Background:
- Rhenium complexes are vital in catalysis and materials science.
- Terminal phosphide and arsenide ligands offer unique electronic properties.
- Understanding metal-pnictogen bonding is crucial for novel compound development.
Purpose of the Study:
- To synthesize and characterize novel rhenium(V) complexes with terminal phosphide (Pn) and arsenide (As) ligands.
- To investigate the reactivity of these complexes, particularly their oxidation and coupling behavior.
- To elucidate the electronic structure and bonding in the resulting Pn-Pn coupled products.
Main Methods:
- Decarbonylation of rhenium(III) pnictaethynolates to form rhenium(V) complexes.
- One-electron oxidation of the synthesized pnictide complexes.
- Spectroscopic characterization (e.g., NMR, IR) and X-ray crystallography.
- Computational bond analysis (e.g., Density Functional Theory).
Main Results:
- Successful isolation of rhenium(V) complexes bearing terminal phosphide and arsenide ligands.
- Observation of Pn-Pn coupling products upon one-electron oxidation of the rhenium(V) complexes.
- Crystallographic and spectroscopic data confirmed the structures of the coupled products.
- Computational analysis indicated the coupled species are best described as {Pn2}0 units stabilized by donor-acceptor interactions.
Conclusions:
- Novel rhenium(V) complexes with terminal phosphide and arsenide ligands were synthesized.
- The Pn-Pn coupling reaction provides a new route to unique {Pn2}0 species.
- Donor-acceptor interactions play a key role in stabilizing these unusual bonding arrangements.
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