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Issue 7, 2011
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Restricting the geometrical relaxation in four-coordinate copper(I) complexes using face-to-face and edge-to-face π-interactions

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Abstract

A series of [Cu(N,N)(P,P)]+, [Cu(N,N)(P,S)]+, [Cu(N,N)2]+ and [Cu(P,S)2]+ complexes incorporating the ligands 2,2′-bipyridine, 1,10-phenanthroline, 1,2-bis(diphenylphosphino)ethane, bis(2-(diphenylphosphino)phenyl)ether (1), 2-diphenylphosphinothioanisole (3) and 2-methyl-6′-phenyl-2,2′-bipyridine (4) has been synthesized and structurally characterized. We have assessed the degree of distortion of two bidentate ligands away from an ideal tetrahedral arrangement about the copper(I) ion using the White model. The greatest distortion along a pathway towards square planar coordination is observed in [Cu(4)2][PF6] and is a result of intra-cation π-stacking between phenyl and bpy domains. Each of the complexes which contain the P,S-chelating ligand 3 exhibits significant ‘rocking’ or ‘wagging’ distortions which are associated with intra-cation CHmethyl⋯π interactions. The extent of this distortion can also be assessed using a less rigorous approach by measuring the S–Cu–X and P–Cu–X angles where the S and P atoms belong to ligand 3, and X is the midpoint of the backbone of the second ligand. [Cu(3)2][PF6] and [Cu(1)(3)][PF6] exhibit embraces between the phenyl substituents that result in the copper(I) ion being sterically protected, and the room temperature 1H NMR solution spectrum of [Cu(1)(3)][PF6] reveals hindered rotation of the phenyl rings of ligand.

Graphical abstract: Restricting the geometrical relaxation in four-coordinate copper(i) complexes using face-to-face and edge-to-face π-interactions

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Publication details

The article was received on 24 Nov 2010, accepted on 24 Jan 2011, published on 16 Feb 2011 and first published online on 16 Feb 2011


Article type: Paper
DOI: 10.1039/C0CE00880J
Citation: CrystEngComm, 2011,13, 2742-2752
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    Restricting the geometrical relaxation in four-coordinate copper(I) complexes using face-to-face and edge-to-face π-interactions

    E. C. Constable, C. E. Housecroft, P. Kopecky, E. Schönhofer and J. A. Zampese, CrystEngComm, 2011, 13, 2742
    DOI: 10.1039/C0CE00880J

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