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Issue 5, 2017
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Reactivity of hydride bridges in a high-spin [Fe3(μ-H)3]3+ cluster: reversible H2/CO exchange and Fe–H/B–F bond metathesis

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Abstract

The triiron trihydride complex Fe3H3L (1) [where L3− is a tris(β-diketiminate)cyclophanate] reacts with CO and with BF3·OEt2 to afford (FeICO)2FeII3-H)L (2) and Fe3F3L (3), respectively. Variable-temperature and applied-field Mössbauer spectroscopy support the assignment of two high-spin (HS) iron(I) centers and one HS iron(II) ion in 2. Preliminary studies support a CO-induced reductive elimination of H2 from 1, rather than CO trapping a species from an equilibrium mixture. This complex reacts with H2 to regenerate 1 under a dihydrogen atmosphere, which represents a rare example of reversible CO/H2 exchange and the first to occur at high-spin metal centers, as well as the first example of a reversible multielectron redox reaction at a designed high-spin metal cluster. The formation of 3 proceeds through a previously unreported net fluoride-for-hydride substitution, and 3 is surprisingly chemically inert to Si–H bonds and points to an unexpectedly large difference between the Fe–F and Fe–H bonds in this high-spin system.

Graphical abstract: Reactivity of hydride bridges in a high-spin [Fe3(μ-H)3]3+ cluster: reversible H2/CO exchange and Fe–H/B–F bond metathesis

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Publication details

The article was received on 21 Dec 2016, accepted on 27 Mar 2017 and first published on 11 Apr 2017


Article type: Edge Article
DOI: 10.1039/C6SC05583D
Citation: Chem. Sci., 2017,8, 4123-4129
  • Open access: Creative Commons BY-NC license
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    Reactivity of hydride bridges in a high-spin [Fe3(μ-H)3]3+ cluster: reversible H2/CO exchange and Fe–H/B–F bond metathesis

    K. J. Anderton, B. J. Knight, A. L. Rheingold, K. A. Abboud, R. García-Serres and L. J. Murray, Chem. Sci., 2017, 8, 4123
    DOI: 10.1039/C6SC05583D

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