The discovery of the all-phosphorus analogues of the well-known Cp ligand and benzene in the complexes [Cp*Fe(η5‑P5)] (1) and [(Cp*Mo)2(µ‑η6:η6‑P6)] (2) by Scherer et al. in the 1980’s can be viewed as a milestone in organometallic chemistry.[1,2] These complexes possess several P atoms with lone pairs and can therefore act as multidentate ligands themselves. Previous investigations enabled the isolation of inorganic fullerene-like supramolecules from reactions of 1 with CuI halides.[3] This talk is focusing on their coordination and redox chemistry involving weakly coordinating anions (WCA’s). It will be shown that the complexes 1 and 2 show very flexible reactivity towards “naked” cations like Cu+, Ag+ and Tl+ (see Fig. 1) which makes them viable multidentate ligands in supramolecular coordination chemistry. A systematical investigation of their reactivity and how it can be controlled will be shown. References: [1] O. Scherer, T. Brück, Angew. Chem. Int. Ed. 1987, 26, 59. [2] O. Scherer, H. Sitzmann, G. Wolmershäuser, Chem. Int. Ed. 1985, 24, 351. [3] J. Bai, A. Virovets, M. Scheer, Science 2003, 300, 781.

Highly dynamic coordination chemistry and redox chemistry of aromatic polyphosphorus complexes

249th National Meeting (2015)

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