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5. A π-Stacked Organometallic Propeller: Experimental and Theoretical Studies on Reactivity and Bonding in the π-Arene-Bridged Nickel Triple-Decker [{(η5-Me4EtC5)Ni}2(μ-η3:η3-decacyclene)]

Author

Schneider, Jörg J., primary, Spickermann, Dirk, additional, Bläser, Dieter, additional, Boese, Roland, additional, Rademacher, Paul, additional, Labahn, Thomas, additional, Magull, Jörg, additional, Janiak, Christoph, additional, Seidel, Naka, additional, and Jacob, Klaus, additional

Published
2001
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8. Synthesis, structure and spectroelectrochemistry of bis(η6-1,4-tri-tert-butyl-benzene)chromium(0) and bis(η5-1,2,4-tri-tert-butyl-cyclopentadienyl)cobalt(II). Dia- and paramagnetic sandwich complexes derived from sterically highly demanding π-ligands

Author

Schneider, Jörg J, primary, Czap, Norbert, additional, Spickermann, Dirk, additional, Lehmann, Christian W, additional, Fontani, Marco, additional, Laschi, Franco, additional, and Zanello, Piero, additional

Published
1999
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11. Decacyclene as Complexation Manifold: Synthesis, Structure and Properties of Its Fe2and Fe4Slipped Triple‐Decker Complexes

Author

Schneider, Jörg J., Spickermann, Dirk, Lehmann, Christian W., Magull, Jörg, Krüger, Hans‐Jörg, Ensling, Jürgen, and Gütlich, Philipp

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‐(η6:η6‐decacyclene)] (3) and [{(η5‐Me4EtC5)Fe}4‐μ4‐(η6:η6:η6:η6‐decacyclene)] (4). Metal complexation in 3and 4occurs 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 4crystallizes in the chiral space group C2221; the investigated crystal only contains decacyclene rings with Mchirality. 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 3and 4, exemplified by potential differences ΔEof 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 3and 4. The sucesssful syntheses of 3and 4together with earlier results from our laboratory proves that all five‐ and six‐membered π subunit sets of 1are prone to metal complexation. A clear site preference in 1towards the complexation of [CpR]iron, ‐cobalt, and ‐nickel fragments exists.

Published
2006
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12. Decacyclene as complexation manifold: synthesis, structure and properties of its Fe2 and Fe4 slipped triple-decker complexes.

Author

Schneider JJ, Spickermann D, Lehmann CW, Magull J, Krüger HJ, Ensling J, and Gütlich P

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.

Published
2006
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