Selective Insertion of Dioxygen into an (η2-C60)−Ir Bond: Synthesis and Structure of the First Metallacyclic Complex with a σ-Coordinated Fullerene Molecule
✍ Scribed by Alexander V. Usatov; Ekaterina V. Martynova; Fedor M. Dolgushin; Alexander S. Peregudov; Mikhail Yu. Antipin; Yurii N. Novikov
- Publisher
- John Wiley and Sons
- Year
- 2003
- Tongue
- English
- Weight
- 132 KB
- Volume
- 2003
- Category
- Article
- ISSN
- 1434-1948
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✦ Synopsis
Abstract
Oxidation of the carboranyliridium fullerene complex [(η^2^‐C~60~)Ir(o‐HCB~10~H~9~CCH~2~PPh~2~‐B,P)(__t__BuNC)~2~] (I) in CHCl~3~ solution by O~2~ occurs by a selective insertion of the dioxygen molecule into the longest Ir−C bond (in the trans‐position relative to the B‐σ‐carboranyl fragment) to give a new metal complex [σ‐C~60~OO‐Ir(o‐HCB~10~H~9~CCH~2~PPh~2~‐B,P)(__t__BuNC)~2~] (II). Complex II was isolated and characterized analytically and by UV, IR, ^1^H and ^31^P NMR spectroscopy. An X‐ray diffraction study of II showed that this complex contains a cyclic iridaperoxide fragment in which the fullerene cage is σ‐coordinated to the iridium atom. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)