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Synthesis of Triazole and Tetrazole-Functionalized Zr-Based Metal-Organic Frameworks Through Post-Synthetic Ligand Exchange
Published on: June 23, 2023
Amido/amine triazacyclononane-based zirconium complexes: syntheses, reactivity, and structures
Humberto Ferreira1, Alberto R Dias, M Teresa Duarte
1Centro de Química Estrutural, Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisboa, Portugal.
Inorganic Chemistry
|January 30, 2007
Summary
New zirconium complexes were synthesized using triamido-triazacyclonane ligands. These reactions demonstrate novel coordination chemistry and the formation of a chiral zirconium center in one complex.
Area of Science:
- Organometallic Chemistry
- Coordination Chemistry
- Zirconium Chemistry
Background:
- Triamido-triazacyclonane ligands offer unique coordination environments for metal centers.
- Zirconium complexes are of interest for catalysis and materials science.
Purpose of the Study:
- To synthesize and characterize novel zirconium complexes with triamido-triazacyclonane ligands.
- To explore the reactivity of these complexes and investigate their structural properties.
Main Methods:
- Reactions of [Zr(NMe2)4]2 with triamido-triazacyclonane precursors.
- Treatment of zirconium complexes with sodium hydride (NaH).
- Reactions of zirconium tetrachloride (ZrCl4) with lithiated or sodiated ligands.
- Reactions with lithium phenylacetylide (LiC≡CPh).
Main Results:
- Formation of zirconium complexes with dianionic tacn-based ligands, featuring coordinated dimethylamido and deprotonated amine arms.
- Synthesis of a complex via N-Si bond cleavage of a pendent arm.
- Preparation of zirconium chloride and zirconium phenylacetylide complexes.
- Solid-state structure of one complex revealed a chiral metal center.
Conclusions:
- Novel zirconium complexes with functionalized triamido-triazacyclonane ligands were successfully synthesized.
- The reactivity studies highlight the versatility of these ligands in zirconium coordination chemistry.
- The discovery of a chiral zirconium center opens possibilities for asymmetric synthesis applications.
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