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Issue 45, 2013
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Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(I) complexes: structures and spectroelectrochemical behaviour

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Abstract

1,2,4,5-Tetracyanobenzene (TCNB) was reacted with [Cu(dppf)(CH3CN)2](BF4) and [Cu(dchpf)(CH3CN)](BF4), dppf = 1,1′-bis(diphenylphosphino)ferrocene and dchpf = 1,1′-bis(dicyclohexylphosphino)ferrocene, to produce a heterotetranuclear metallamacrocycle 1, {[Cu(dppf)(μ-TCNB)](BF4)}2, and a heterooctanuclear complex 2, [{Cu(dchpf)}44-TCNB)](BF4)4. Complex 1 is the first example of a structurally characterised discrete transition metal complex of TCNB. Upon crystallisation attempts, compound 2 formed the structurally identified coordination polymer 3, {[Cu(dchpf)(μ-TCNB)]2(BF4)2}n. Structural and spectroscopic analyses confirmed the redox-innocent behaviour of TCNB in 1, 2 and 3. However, the soluble compounds 1 and 2 could be oxidised and reduced spectroelectrochemically (UV-vis, IR, and EPR). The oxidation occurs invariably at the ferrocene sites without notable splitting of redox potentials. Reduction involves the TCNB bridging ligands to produce radical complexes. As a variably bridging acceptor component of supramolecular structures the TCNB ligand thus adopts an intermediate position between the highly electron transfer-active TCNE, TCNQ and TCNQF4 systems and the numerous redox-innocent bridges.

Graphical abstract: Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(i) complexes: structures and spectroelectrochemical behaviour

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Publication details

The article was received on 24 May 2013, accepted on 19 Aug 2013 and first published on 19 Aug 2013


Article type: Paper
DOI: 10.1039/C3DT51360B
Citation: Dalton Trans., 2013,42, 16142-16150
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    Variable coordination of redox-active TCNB in discrete and polymeric ferrocenylcopper(I) complexes: structures and spectroelectrochemical behaviour

    R. Jana, S. M. Mobin, B. Schwederski, J. Fiedler and W. Kaim, Dalton Trans., 2013, 42, 16142
    DOI: 10.1039/C3DT51360B

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