Synthesis of Zirconium Aryloxide Complexes Containing Pendent Vinyl Groups

Area of Science:

• Organometallic Chemistry
• Coordination Chemistry
• Materials Science

Background:

• Zirconium complexes are versatile in catalysis and materials science.
• Incorporating olefin functionalities into ligands offers pathways for further chemical modification.
• Developing efficient synthetic routes to novel organozirconium compounds is crucial for exploring their applications.

Purpose of the Study:

• To describe the synthesis of oxygen-ligated zirconium complexes bearing pendent olefin groups.
• To explore the reactivity of olefin-substituted phenols and alcohols with zirconium reagents.
• To characterize novel zirconium complexes with potential applications in catalysis or materials.

Main Methods:

• Reactions of zirconium precursors (e.g., [Zr(O(i)Pr)(4)(HO(i)Pr)](2), [Zr(NMe(2))(4)](2), "Zr(OEt)(4)") with olefin-substituted phenols (eugenol) and alcohols.
• Isolation and purification of synthesized zirconium complexes.
• Crystallographic characterization of three distinct complexes.

Main Results:

• Successful synthesis of three crystallographically characterized zirconium complexes in 55-90% yield.
• Complex 1: [((i)PrO)(2)(ArO)Zr(&mgr;-O(i)Pr)](2) formed from eugenol and [Zr(O(i)Pr)(4)(HO(i)Pr)](2).
• Complex 2: A mixed ligand salt {Me(2)NH(2)}{[(2,6-Me(2)C(6)H(3)O)(3)Zr](2)(&mgr;-OCH(2)CH=CH(2))(3)} synthesized using allyl alcohol and 2,6-dimethylphenol.
• Complex 3: [K(2)Zr(OAr)(4)(OEt)](2)(O) obtained from the potassium salt of eugenol and "Zr(OEt)(4)".

Conclusions:

• Demonstrated efficient methods for attaching pendent olefin groups to oxygen-ligated zirconium centers.
• Synthesized novel organozirconium complexes with diverse structures and high yields.
• The reported complexes serve as valuable building blocks for further synthetic elaborations and potential applications.