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Issue 42, 2008
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A tetranuclear organorhenium(I) complex of the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane radical anion, TCNQF4˙

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Abstract

The radical complex {(μ4-TCNQF4)[Re(CO)3(bpy)]4}(PF6)3, as prepared and isolated from the reaction between TCNQF4 and [Re(CO)3(bpy)(MeOH)](PF6), was studied electrochemically and by IR vibrational spectroscopy, UV-Vis-NIR absorption spectroscopy, and by EPR at 9.5, 190 and 285 GHz. The isotropic g factor of 2.0058, the detectable g anisotropy, and the 185,187Re EPR hyperfine coupling of 0.95 mT for four equivalent metal nuclei support predominant, but not exclusive, spin localisation at the bridging ligand. Nitrile and metal carbonyl stretching frequencies as well as the typically structured near infrared absorption band lend further support to (TCNQF4˙)(ReI)4 as the most appropriate oxidation state formulation. In comparison to the non-radical complex {(μ4-TCNQ)[Re(CO)3(bpy)]4}(PF6)4 an X-ray structure analysis of {(μ4-TCNQF4)[Re(CO)3(bpy)]4}(PF6)3 shows a marginally more twisted (ReNCCCNRe)(C6X4)(ReNCCCNRe) configuration and a different up/down arrangement of the [Re(CO)3(bpy)]+ groups. This first isolation, electrochemical, structural and spectroscopic characterisation of a discrete tetranuclear radical complex of a TCNQ-type ligand suggests a link between the stability of such materials and the rather small structural changes on ligand-based electron transfer.

Graphical abstract: A tetranuclear organorhenium(i) complex of the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane radical anion, TCNQF4˙−

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Publication details

The article was received on 09 May 2008, accepted on 04 Jul 2008 and first published on 08 Sep 2008


Article type: Paper
DOI: 10.1039/B807977C
Citation: Dalton Trans., 2008,0, 5749-5753
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    A tetranuclear organorhenium(I) complex of the 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-p-quinodimethane radical anion, TCNQF4˙

    A. N. Maity, B. Sarkar, M. Niemeyer, M. Sieger, C. Duboc, S. Zalis and W. Kaim, Dalton Trans., 2008, 0, 5749
    DOI: 10.1039/B807977C

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