Decacyclene as complexation manifold: synthesis, structure and properties of its Fe2 and Fe4 slipped triple-decker complexes |
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Authors: | Schneider Jörg J Spickermann Dirk Lehmann Christian W Magull Jörg Krüger Hans-Jörg Ensling Jürgen Gütlich Philipp |
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Institution: | Fachbereich Chemie, Eduard-Zintl-Institut für Anorganische und Physikalische Chemie, TU Darmstadt, Petersenstrasse 18, 64287 Darmstadt, Germany. joerg.schneider@ac.chemie.tu-darmstadt.de |
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Abstract: | Reaction of (eta(5)-Me4EtC5)Fe(II)Cl(tmeda)] (tmeda = N,N,N'N'-tetramethylethylenediamine) with a polyanion solution of decacyclene (1) results in the formation of the triple-deckers {(eta(5)-Me4EtC5)Fe}2-mu2-(eta(6):eta(6)-decacyclene)] (3) and {(eta(5)-Me4EtC5)Fe}4-mu4-(eta(6):eta(6):eta(6):eta(6)-decacyclene)] (4). Metal complexation in 3 and 4 occurs on opposite faces of the pi 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 C222(1); 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 deltaE 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 successful syntheses of 3 and 4 together with earlier results from our laboratory proves that all five- and six-membered pi subunit sets of 1 are prone to metal complexation. A clear site preference in 1 towards the complexation of Cp(R)]iron, -cobalt, and -nickel fragments exists. |
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Keywords: | arene ligands coordination modes electrochemistry iron sandwich complexes |
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