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Issue 1, 2013
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Access to formally Ni(I) states in a heterobimetallic NiZn system

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Heterobimetallic NiZn complexes featuring metal centers in distinct coordination environments have been synthesized using diimine–dioxime ligands as binucleating scaffolds. A tetramethylfuran-containing ligand derivative enables a stable one-electron-reduced S = 1/2 species to be accessed using Cp2Co as a chemical reductant. The resulting pseudo-square planar complex exhibits spectroscopic and crystallographic characteristics of a ligand-centered radical bound to a Ni(II) center. Upon coordination of a π-acidic ligand such as PPh3, however, a five-coordinate Ni(I) metalloradical is formed. The electronic structures of these reduced species provide insight into the subtle effects of ligand structure on the potential and reversibility of the NiII/I couple for complexes of redox-active tetraazamacrocycles.

Graphical abstract: Access to formally Ni(i) states in a heterobimetallic NiZn system

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The article was received on 10 Aug 2012, accepted on 10 Sep 2012 and first published on 12 Sep 2012

Article type: Edge Article
DOI: 10.1039/C2SC21231E
Citation: Chem. Sci., 2013,4, 157-163

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    Access to formally Ni(I) states in a heterobimetallic NiZn system

    C. Uyeda and J. C. Peters, Chem. Sci., 2013, 4, 157
    DOI: 10.1039/C2SC21231E

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