Sodium naphthalenide reduction of 1,3–diphenyl–6–(tert-butyl) fulvene: Stabilizing Eu2+ with a sterically demanding ansa–ligand framework
| Autor: | Gary J. Balaich, Sonya K. Adas |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
Steric effects
Cyclopentadiene 010405 organic chemistry Ligand Organic Chemistry Sodium naphthalenide 010402 general chemistry 01 natural sciences Biochemistry Medicinal chemistry 0104 chemical sciences Inorganic Chemistry chemistry.chemical_compound Cyclopentadienyl complex chemistry Materials Chemistry Salt metathesis reaction Physical and Theoretical Chemistry Metallocene Fulvene |
| Zdroj: | Journal of Organometallic Chemistry. 857:200-206 |
| ISSN: | 0022-328X |
| DOI: | 10.1016/j.jorganchem.2017.12.008 |
| Popis: | Stereoselective syntheses of three new rac di–(tert–butyl)ethano bridged metallocene compounds of Yb, Eu and Sm were carried out by a unique strategy involving hydrocarbon radical anion coupling of a trisubstituted pentafulvene followed by incorporation of the metal by K+ salt metathesis reactions. Reductive coupling of 1,3–diphenyl–6–(tert-butyl) fulvene with sodium naphthalenide gave the corresponding bis(cyclopentadiene) ansa–ligand precursor rac–[(CHBut)2(Ph2C5H3)2] HL. Subsequent reaction of HL with KN(SiMe3)2 afforded the corresponding di–potassium salt complex [(CHBut)2(Ph2C5H2)2]K2(THF)3 1. Reactions of 1 with LnI2 (Ln = Yb, Eu, Sm) afforded new lanthanide ansa–metallocenes, [(CHBut)2(Ph2C5H2)]2Yb(DME) 2, [(CHBut)2(Ph2C5H2)]2Eu(DME)2 3 and [(CHBut)2(Ph2C5H2)]2Sm(DME)2 4 in good yields. The ansa–europocene 3 is the first example of a Eu2+ ion complexed by an ethano–bridged cyclopentadienyl ligand. This work underscores the usefulness of hydrocarbon radical anion coupling in the construction of sterically demanding Ph2Cp based ansa–ligand frameworks for d- and f-block metallocenes. |
| Databáze: | OpenAIRE |
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