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Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′-Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LMII2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII2)2(O2CC5H4)2Fe]2+ Complexes (M=Co, Ni, Zn)

  1. Vasile Lozan Dr.1,
  2. Axel Buchholz Dr.2,
  3. Winfried Plass Prof. Dr.2,
  4. Berthold Kersting Prof. Dr.1

Article first published online: 19 JUN 2007

DOI: 10.1002/chem.200700107

Issue

Chemistry - A European Journal

Chemistry - A European Journal

Volume 13, Issue 26, pages 7305–7316, September 7, 2007

Additional Information

How to Cite

Lozan, V., Buchholz, A., Plass, W. and Kersting, B. (2007), Dinuclear Amine–Thiophenolate Complexes Coligated by Ferrocenemonocarboxylate and 1,1′-Ferrocenedicarboxylate Anions: Preparation, Characterization and Structures of Trinuclear [LMII2(O2CC5H4FeCp)]+ and Pentanuclear [(LMII2)2(O2CC5H4)2Fe]2+ Complexes (M=Co, Ni, Zn). Chemistry - A European Journal, 13: 7305–7316. doi: 10.1002/chem.200700107

Author Information

  1. 1

    Institut für Anorganische Chemie, Universität Leipzig, Johannisallee 29, 04103 Leipzig, Germany, Fax: (+49) 341-973-6199

  2. 2

    Institut für Anorganische und Analytische Chemie, Friedrich-Schiller Universität Jena, Carl-Zeiss-Promenade 10, 07745 Jena, Germany

Publication History

  1. Issue published online: 29 AUG 2007
  2. Article first published online: 19 JUN 2007
  3. Manuscript Received: 23 JAN 2007

Funded by

  • Deutsche Forschungsgemeinschaft. Grant Number: SPP 1137 “Molecular Magnetism”, KE 585/4-3,2,1
  • Universät Leipzig

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Keywords:

  • binuclear complexes;
  • ferrocene;
  • magnetic properties;
  • polynuclear complexes;
  • redox chemistry

Graphical Abstract

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Multinuclear complexes: A series of tri- and pentanuclear transition-metal complexes in which pairs of dinuclear nickel(II) (see figure) or cobalt(II) complexes are coligated by ferrocenecarboxylate or 1,1′-ferrocenedicarboxylate dianions have been prepared and structurally characterized.

Abstract

A series of novel tri- and pentanuclear complexes composed of dinuclear LM2 units (M=Co, Ni, Zn; L=24-membered macrocyclic hexaazadithiophenolate ligand) and ferrocenecarboxylate ([CpFeC5H4CO2]−) or 1,1′-ferrocenedicarboxylate ([Fe(C5H4CO2)2]2−) groups is reported. The complexes [LMII2(O2CC5H4FeCp)]+ (M=Co (6), Ni (7), Zn (8)) and [(LMII2)2(O2CC5H4)2Fe]2+ (M=Co (9), Ni (10)) have been prepared by substitution reactions from labile [LMII2L′]+ precursors (L′=Cl, OAc) and the respective ferrocenecarboxylate anions in methanol. Mixed-valent [(LCoIICoIII)2(O2CC5H4)2Fe]4+ (11) was prepared by oxidation of 9 with bromine. Complexes 7[BPh4], 8[BPh4], 9[BPh4]2, 10[BPh4]2, and 11[ClO4]4 have been characterized by X-ray crystallography; showing that the ferrocenyl carboxylates act as bidentate (7, 8) or bis-bidentate (9–11) bridging ligands towards one or two bioctahedral LM2 subunits, respectively. The structures are retained in solution as indicated by NMR spectroscopic studies on the diamagnetic Zn2Fe complex 8[ClO4]. Electrochemical studies reveal significant anodic potential shifts for the oxidation potential of the ferrocenyl moieties upon complexation and the magnitude of the potential shift appears to correlate with the charge of the LM2 subunits. This is qualitatively explained in terms of destabilizing electrostatic (Coulomb) interactions between the M2+ ions of the LM2 unit and the proximate ferrocenium fragment. An analysis of the temperature-dependent magnetic susceptibility data for 10[BPh4]2 shows the presence of weak ferromagnetic magnetic exchange interactions between the NiII ions in the LNi2 units. The exchange coupling across the ferrocenedicarboxylate bridge is negligible.

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