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Issue 21, 2000
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A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands

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Abstract

A geometrical analysis has been performed on π–π stacking in metal complexes with aromatic nitrogen-containing ligands based on a Cambridge Structural Database search and on X-ray data of examples in the recent literature. It is evident that a face-to-face π–π alignment where most of the ring-plane area overlaps is a rare phenomenon. The usual π interaction is an offset or slipped stacking, i.e. the rings are parallel displaced. The ring normal and the vector between the ring centroids form an angle of about 20° up to centroid–centroid distances of 3.8 Å. Such a parallel-displaced structure also has a contribution from π–σ attraction, the more so with increasing offset. Only a limited number of structures with a near to perfect facial alignment exists. The term π–π stacking is occasionally used even when there is no substantial overlap of the π-ring planes. There is a number of metal–ligand complexes where only the edges of the rings interact in what would be better described a C–H  π attraction.

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Publication details

The article was received on 14 Apr 2000, accepted on 21 Jun 2000 and first published on 22 Sep 2000


Article type: Paper
DOI: 10.1039/B003010O
Citation: J. Chem. Soc., Dalton Trans., 2000, 3885-3896
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    A critical account on π–π stacking in metal complexes with aromatic nitrogen-containing ligands

    C. Janiak, J. Chem. Soc., Dalton Trans., 2000, 3885
    DOI: 10.1039/B003010O

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