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Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe2 and Fe4 Slipped Triple‐Decker Complexes

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Lehmann,  Christian W.
Service Department Lehmann (EMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Schneider, J. J., Spickermann, D., Lehmann, C. W., Magull, J., Krüger, H.-J., Ensling, J., et al. (2006). Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe2 and Fe4 Slipped Triple‐Decker Complexes. Chemistry – A European Journal, 12(5), 1427-1435. doi:10.1002/chem.200500100.


Cite as: http://hdl.handle.net/11858/00-001M-0000-000F-93A5-A
Abstract
Reaction of [(η5‐Me4EtC5)FeIICl(tmeda)] (tmeda=N,N,N′N′‐tetramethylethylenediamine) with a polyanion solution of decacyclene (1) results in the formation of the triple‐deckers [{(η5‐Me4EtC5)Fe}2‐μ2‐(η66‐decacyclene)] (3) and [{(η5‐Me4EtC5)Fe}4‐μ4‐(η6666‐decacyclene)] (4). Metal complexation in 3 and 4 occurs on opposite faces of the π perimeter in an alternating mode. The decacyclene ring adopts a gently twisted molecular propeller geometry with twofold crystallographic symmetry (C2). Complex 4 crystallizes in the chiral space group C2221; the investigated crystal only contains decacyclene rings with M chirality. The handedness can be assigned unambiguously to the presence of the iron atoms. Cyclovoltammetric studies revealed quasireversible behavior of the redox events and a strong interaction of the Fe atoms in 3 and 4, exemplified by potential differences ΔE of 660 and 770(780) mV between the first and the second individual oxidation processes. This corresponds to a high degree of metal–metal interaction for 3 and 4. The sucesssful syntheses of 3 and 4 together with earlier results from our laboratory proves that all five‐ and six‐membered π subunit sets of 1 are prone to metal complexation. A clear site preference in 1 towards the complexation of [CpR]iron, ‐cobalt, and ‐nickel fragments exists.