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Macrocycles containing 1,1'-ferrocenyldiselenolato ligands on group 4 metallocenes
Clara Sanchez-Perez1, Caroline E Knapp2, Minna M Karjalainen3
1Laboratory of Inorganic Chemistry, Environmental and Chemical Engineering, University of Oulu, P. O. Box 3000, FI-90014 Oulu, Finland and Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK. c.j.carmalt@ucl.ac.uk.
Dalton Transactions (Cambridge, England : 2003)
|March 29, 2018
Summary
New macrocyclic tetranuclear complexes containing iron and transition metals (M = Ti, Zr, Hf) were synthesized. These complexes decompose into FexMSe2, showing potential as single-source precursors for advanced functional materials.
Area of Science:
- Organometallic Chemistry
- Materials Science
- Coordination Chemistry
Background:
- Macrocyclic complexes offer unique structural and electronic properties.
- Iron and early transition metal complexes are of interest for materials applications.
- Selenium-bridged metal centers present novel synthetic targets.
Purpose of the Study:
- To synthesize and characterize novel macrocyclic tetranuclear complexes.
- To investigate the structural and thermal decomposition properties of these complexes.
- To explore their potential as single-source precursors for functional materials.
Main Methods:
- Synthesis of macrocyclic iron-metal complexes.
- Characterization using 77Se NMR spectroscopy.
- Structural determination via single-crystal X-ray diffraction.
- Thermal decomposition analysis using thermogravimetric analysis (TGA).
- Product identification using powder X-ray diffraction.
Main Results:
- Successfully prepared five macrocyclic tetranuclear complexes: [Fe(η5-C5H4Se)2M(η5-C5H4R)2]2 where M = Ti, Zr, Hf and R = H or tBu.
- Established the mutually similar macrocyclic structures linked by selenium bridges.
- Observed a two-step thermal decomposition yielding FexMSe2 as final products.
- Confirmed structural similarity between complexes 1-3 and 5, and isomorphous nature of 4 with 5.
Conclusions:
- The synthesized macrocyclic complexes exhibit well-defined tetranuclear structures.
- Thermal decomposition provides a pathway to FexMSe2 materials.
- These compounds are promising single-source precursors for the fabrication of functional inorganic materials.