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Issue 41, 2010
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Synthesis and characterization of a series of halide-bridged, multinuclear iron(II) and cobalt(II) diamido complexes and a dinuclear, high-spin cobalt(II) alkyl derivative

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Abstract

The synthesis and structural characterization of four multinuclear, halide-bridged iron(II) and cobalt(II) diamidosilylether complexes of the form{Fe2Br2[tBuNON]}2 (1), {Co2Br2[tBuNON]}2 (2), {Fe2Cl2[tBuNON]}n (3) and {Co2Cl2[tBuNON](LiCl)·2THF}2 (4) ([tBuNON]2 = [Me3CN(SiMe2)]2O2−) are reported. Thus, reaction of one equivalent of Li2[tBuNON] with two equivalents of MX2 (X = Cl or Br; M = Co or Fe) form 1–4, which structurally contain one diamido ligand bridging two metal centres. Each amido group interacts with both metal centres to yield binuclear M2X2[tBuNON] units which dimerize via bromide bridges to form tetranuclear {Fe2Br2[tBuNON]}2 (1) and {Co2Br2[tBuNON]}2 (2) or form an infinite 1D chain of chloride-bridged dinuclear clusters {Fe2Cl2[tBuNON]}n (3). Replacing bromide for chloride in 2 results in a tetranuclear “ate” complex {Co2Cl2[tBuNON](LiCl)·2THF}2 (4) in which the tetranuclear core is capped with one LiCl and two THF molecules on each side. The reaction of four equivalents of LiCH2SiMe3 with 4 generated the high-spin cobalt(II) alkyl complex {Co2(CH2SiMe3)2[tBuNON]} (5), in which each amide in [tBuNON]2 bridges two Co(II) centres, but the silylether donor only binds to one metal; each Co(II) centre has a terminal –CH2SiMe3 unit bonded as well. Variable temperature (1.8–300 K) magnetic susceptibility data for 1–5 showed significant antiferromagnetic coupling between metal centres.

Graphical abstract: Synthesis and characterization of a series of halide-bridged, multinuclear iron(ii) and cobalt(ii) diamido complexes and a dinuclear, high-spin cobalt(ii) alkyl derivative

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Publication details

The article was received on 22 May 2010, accepted on 14 Jul 2010 and first published on 20 Sep 2010


Article type: Paper
DOI: 10.1039/C0DT00524J
Citation: Dalton Trans., 2010,39, 9889-9896
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    Synthesis and characterization of a series of halide-bridged, multinuclear iron(II) and cobalt(II) diamido complexes and a dinuclear, high-spin cobalt(II) alkyl derivative

    Z. Moatazedi, M. J. Katz and D. B. Leznoff, Dalton Trans., 2010, 39, 9889
    DOI: 10.1039/C0DT00524J

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