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Published on: August 12, 2019
Iron in a trigonal tris(alkoxide) ligand environment
Matthew B Chambers1, Stanislav Groysman, Dino Villagrán
1Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
Inorganic Chemistry
|February 26, 2013
Summary
Iron(II) and iron(III) complexes with a tris(ditox) ligand were synthesized. The iron(II) complex reacts with oxidants to form a reactive intermediate that cleaves C-H bonds, unlike the iron(III) complex.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
Background:
- Mononuclear iron complexes are crucial in various catalytic processes.
- Understanding the reactivity of iron complexes with different oxidation states is key to designing new catalysts.
Purpose of the Study:
- To synthesize and characterize mononuclear iron(II) and iron(III) complexes with a trigonal tris(ditox) ligand.
- To investigate the reactivity of these complexes towards oxidants and their potential in C-H bond activation and oxidation reactions.
Main Methods:
- Synthesis and characterization of mononuclear Fe(II) and Fe(III) complexes using tris(ditox) ligands.
- Reactivity studies with oxidants like PhIO and Me3NO in various solvents.
- Investigation of C-H bond cleavage and oxidation of phosphines.
Main Results:
- The Fe(III) ditox complex showed limited reactivity with oxidants.
- The Fe(II) ditox complex rapidly reacted with oxidants to form a reactive intermediate.
- This intermediate was capable of C-H bond cleavage and phosphine oxidation.
- Reaction rates were influenced by a weak ligand field from the tris(alkoxide) environment.
Conclusions:
- The tris(ditox) ligand environment significantly influences the reactivity of iron complexes.
- The Fe(II) complex can generate a reactive intermediate for C-H activation and oxidation.
- The weak ligand field is crucial for the observed fast reaction rates.
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