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Synthesis, Characterization, and Reactivity of Furan- and Thiophene-Functionalized Bis(N-heterocyclic carbene) Complexes of Iron(II)

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    Synthesis, Characterization, and Reactivity of Furan- and Thiophene-Functionalized Bis(N-heterocyclic carbene) Complexes of Iron(II)
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    † Chair of Inorganic Chemistry/Molecular Catalysis, Catalysis Research Center, Technische Universität München, Ernst-Otto-Fischer-Straße 1, D-85747 Garching, Germany
    ‡ Catalysis Center, King Abdullah University of Science and Technology (KAUST), Thuwal 23955-6900, Kingdom of Saudi Arabia
    *Tel: +49 89 289 13096. E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2014, 53, 18, 9598–9606
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    https://doi.org/10.1021/ic500959m
    Published September 4, 2014
    Copyright © 2014 American Chemical Society
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    Abstract

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    The synthesis of iron(II) complexes bearing new heteroatom-functionalized methylene-bridged bis(N-heterocyclic carbene) ligands is reported. All complexes are characterized by single-crystal X-ray diffraction (SC-XRD), nuclear magnetic resonance (NMR) spectroscopy, and elemental analysis. Tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (2a) and tetrakis(acetonitrile)-cis-[bis(o-imidazol-2-ylidenethiophene)methane]iron(II) hexafluorophosphate (2b) were obtained by aminolysis of [Fe{N(SiMe3)2}2(THF)] with furan- and thiophene-functionalized bis(imidazolium) salts 1a and 1b in acetonitrile. The SC-XRD structures of 2a and 2b show coordination of the bis(carbene) ligand in a bidentate fashion instead of a possible tetradentate coordination. The four other coordination sites of these distorted octahedral complexes are occupied by acetonitrile ligands. Crystallization of 2a in an acetone solution by the slow diffusion of Et2O led to the formation of cis-diacetonitriledi[bis(o-imidazol-2-ylidenefuran)methane]iron(II) hexafluorophosphate (3a) with two bis(carbene) ligands coordinated in a bidentate manner and two cis-positioned acetonitrile molecules. Compounds 2a and 2b are the first reported iron(II) carbene complexes with four coordination sites occupied by solvent molecules, and it was demonstrated that those solvent ligands can undergo ligand-exchange reactions.

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    Supporting Information

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    X-ray crystallographic data in CIF format (CCDC 997386–997389), DFT-optimized geometries of mono-PMe3 derivatives of 2a as xyz coordinates, ORTEP representation of the complex [Fe(dmpe)2(MeCN)2], and additional 1H, 13C, 31P, and HMQC 2D NMR spectra. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2014, 53, 18, 9598–9606
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic500959m
    Published September 4, 2014
    Copyright © 2014 American Chemical Society
    Request reuse permissions

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