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Dioxygen Splitting by a Tantalum(V) Complex Ligated by a Rigid, Redox Non-Innocent Pincer Ligand
Jack Underhill1, Eric S Yang1, Till Schmidt-Räntsch2
1Chemistry Research Laboratory, Department of Chemistry, University of Oxford, 12 Mansfield Rd., Oxford, OX1 3TA, United Kingdom.
Chemistry (Weinheim an Der Bergstrasse, Germany)
|October 25, 2022
Summary
Researchers synthesized a novel tantalum(V) complex and studied its reaction with dioxygen. This reaction yielded a unique oxido-bridged bimetallic complex with an open-shell ground state, showcasing a new pathway for oxygen activation.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
- Materials Science
Background:
- Tantalum complexes are valuable in catalysis and materials science.
- Understanding oxygen activation mechanisms is crucial for developing new chemical transformations.
Purpose of the Study:
- To synthesize and characterize a novel tantalum(V) complex.
- To investigate the reaction of this complex with dioxygen and elucidate the oxygen activation mechanism.
Main Methods:
- Synthesis of tantalum(V) complex [TaCl2(NNNcat)].
- Reaction with dioxygen to form oxido-bridged bimetallic complex [{TaCl2(NNNsq)}2O].
- Characterization using single crystal X-ray diffraction, LIFDI mass spectrometry, NMR, EPR, IR, and UV/VIS/NIR spectroscopy.
- Density Functional Theory (DFT) calculations to investigate reaction mechanisms.
Main Results:
- Formation of the oxido-bridged bimetallic complex [{TaCl2(NNNsq)}2O].
- The dinuclear complex exhibits an open-shell ground state due to partial ligand oxidation.
- DFT calculations revealed a mechanism involving initial O2 binding followed by O2 scission to a terminal oxido-complex.
Conclusions:
- A novel oxido-bridged bimetallic tantalum complex was synthesized and characterized.
- The study provides insights into a new pathway for dioxygen activation by tantalum complexes.
- The findings contribute to the understanding of metal-ligand interactions and redox processes in organometallic chemistry.
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