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Published on: November 9, 2019
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Synthesis, characterization, and alkoxide transfer reactivity of dimeric Tl2(OR)2 complexes
Amanda Grass1, Lakshani Wathsala Kulathungage, Duleeka Wannipurage
1Department of Chemistry, Wayne State University, 5101 Cass Ave., Detroit, MI 48202, USA. groysman@wayne.edu.
Dalton Transactions (Cambridge, England : 2003)
|January 30, 2021
Summary
This study introduces a novel thallium alkoxide complex, Tl₂(OCᵗBu₂Ph)₂, enabling the synthesis of various metal alkoxide complexes. It also demonstrates unique reactivity with ruthenium precursors, including C-H activation.
Area of Science:
- Organometallic Chemistry
- Inorganic Chemistry
Background:
- Homoleptic thallium alkoxide complexes are rare.
- Two-coordinate metal centers in such complexes are unusual.
- Synthesis of specific metal alkoxide complexes can be challenging.
Purpose of the Study:
- To synthesize and characterize a novel homoleptic thallium alkoxide complex.
- To explore the utility of this thallium complex as a precursor for other metal alkoxides.
- To investigate the reactivity of thallium alkoxides with transition metal precursors.
Main Methods:
- Reaction of LiOCᵗBu₂Ph with TlPF₆ to form Tl₂(OCᵗBu₂Ph)₂.
- Characterization using NMR spectroscopy (¹H and ¹³C) and X-ray crystallography.
- Reactions with various metal precursors (Cr, Fe, Cu, Zn, Ru).
Main Results:
- Successful synthesis and characterization of dimeric thallium alkoxide Tl₂(OCᵗBu₂Ph)₂ with two isomers.
- Tl₂(OCᵗBu₂Ph)₂ serves as a precursor for diverse metal alkoxide complexes, including a T-shaped Zn complex.
- Ruthenium alkoxide formation involves C-H activation and bidentate coordination of the alkoxide ligand.
- A related thallium alkoxide, Tl₂(OCᵗBu₂(3,5-Me₂C₆H₃))₂, was also synthesized and showed similar reactivity.
Conclusions:
- The synthesized thallium alkoxide is a versatile precursor for various metal complexes.
- The study highlights unique reactivity patterns, such as C-H activation in ruthenium complexes.
- This work expands the scope of accessible metal alkoxide structures and synthetic methodologies.
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