Expanding the Scope: Monopentafulvene and -Benzofulvene Complexes of Zirconium and Hafnium
2018; American Chemical Society; Volume: 37; Issue: 3 Linguagem: Inglês
10.1021/acs.organomet.7b00832
ISSN1520-6041
AutoresMalte Fischer, Tim Oswald, Hanna Ebert, Marc Schmidtmann, Rüdiger Beckhaus,
Tópico(s)Organometallic Complex Synthesis and Catalysis
ResumoThe reaction of Cp*MCl3 (M = Zr, Zr1; M = Hf, Hf1) with the reducing agent Na/Hg (20% Na) and with sterically encumbered pentafulvenes adamantylidenepentafulvene AdFv, 6,6′-di-p-tolylpentafulvene pTol2Fv, and benzofulvenes adamantylidenebenzofulvene AdBzFv, 10,10′-di-p-tolylbenzofulvene pTol2BzFv, and 10,10′-diphenylbenzofulvene Ph2BzFv yielded the corresponding pentafulvene complexes (η5-pentamethylcyclopentadienyl)metal(η5:η1-pentafulvene)chloride (Zr2a,b, Hf2a,b) and benzofulvene complexes (η5-pentamethylcyclopentadienyl)metal(η5:η1-benzofulvene)chloride (Zr3a–c, Hf3a). This reductive complexation approach can be used in a multigram scale and mostly very good yields (up to 92%). In addition to NMR spectroscopic analyses, the pentafulvene complex Zr2b and benzofulvene complex Zr3b were characterized by X-ray crystallography, showing mainly the π–η5:σ–η1 dianionic bonding mode together with slight influence of the π–η2:π–η3:σ–η1 bonding mode. By use of the prochiral benzofulvenes the corresponding complexes Zr3a–c and Hf3a are furthermore obtained in a diastereoselective manner.
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