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- Title
Vanadium Pentafulvene Complexes: Synthon for Unprecedented Vanadocene<sup>III</sup> Derivatives.
- Authors
de Graaff, Simon; Schwitalla, Kevin; Thye, Hermann; Yusufzadeh, Zainab; Willms, Michael; Schmidtmann, Marc; Beckhaus, Rüdiger
- Abstract
The benzene ligand at CpV(η6--C6H6) (1) is exchanged for pentafulvenes. Using sterically demanding pentafulvenes gives a clean exchange reaction, yielding vanadium pentafulvene (2a and 2b) and benzofulvene complexes (3a and 3b). The molecular structures of the target compounds suggest a π-η5:σ-η¹ coordination mode with a vanadiumIII center. With the sterically low demanding 6,6-dimethylpentafulvene, a C--H activation at the leaving ligand is observed, yielding the ring-substituted vanadoceneII 4. The reactivity of the pentafulvene complexes was investigated. A series of unprecedented vanadoceneIII compounds were synthesized: Under mild conditions, E--H splitting of 4- tert-butylphenol, diphenylamine, and 2,6-diisopropylaniline yield well characterized examples of rare vanadoceneIII phenolate and amide complexes. Insertion reactions into the V--Cexo bond of the pentafulvene complexes by multiple bond containing substrates were found for acetone, 4-chlorobenzonitril and N,N'-dicyclohexylcarbodiimide.
- Subjects
VANADIUM; AMIDES; EXCHANGE reactions; MOLECULAR structure; PHENOXIDES; DIPHENYLAMINE
- Publication
Chemistry - A European Journal, 2023, Vol 29, Issue 29, p1
- ISSN
0947-6539
- Publication type
Article
- DOI
10.1002/chem.202203846