Reaction Chemistry of Zirconocene(II) with Ferrocenyl Carbonyls§
Year: 2025
Type: article
Abstract: Treatment of {Zr}(η2‐Me3SiC≡CSiMe3)(py) ({Zr}=Zr(η5‐C5H5)2; py=C5H5N) (1) with FcC(O)H (Fc=Fe(η5‐C5H5)(η5‐C5H4)) (2 a) gives dimeric [{Zr}(η2‐OCHFc)]2 (3), while the reaction of 1 with ketone FcC(O)Ph (2 b) produces monomeric metallaoxiran [{Zr}(η2‐OCPhFc)(Ph)] (4). In contrast, compound 1 forms [{Zr}(O=CFc2)2] (5) in presence of FcC(O)Fc (2 c). The structures of 3–5 in the solid state were determined by single crystal X‐ray analysis. In 3 two {Zr}(η2‐OCHFc) building blocks are connected to each other over oxygen bridges with the aldehydes being η2‐coordinated. By exchanging aldehyde 2 a by ketone 2 b, monomeric 4 is accessible with a σ‐bonded phenylate ligand and a ketone bonded in a η2‐fashion to Zr(IV). In contrast, within 5 two Fc2C=O ketones are datively bonded to a zirconocene unit with Zr in the oxidation state II, demonstrating a new family of compounds in which metallocene ketones are coordinated to a group 4 metal. Further, compounds 3–5 were characterized by IR spectroscopy and 3, 4 were investigated by matrix assisted laser desorption/ionization mass spectrometry. In case of 5, its crystallisation was tracked by NMR spectroscopy and its reaction towards CH2Cl2 was investigated by high resolution mass spectrometry.
Institution: Chemnitz University of Technology
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,050
OpenAlex ID: W4408338691