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Restricting the geometrical relaxation in four-coordinate copper(I) complexes using face-to-face and edge-to-face pi-interactions

Constable, Edwin C. and Housecroft, Catherine E. and Kopecky, Peter and Schoenhofer, Ewald and Zampese, Jennifer A.. (2011) Restricting the geometrical relaxation in four-coordinate copper(I) complexes using face-to-face and edge-to-face pi-interactions. CrystEngComm, 13 (7). pp. 2742-2752.

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Official URL: http://edoc.unibas.ch/dok/A5848941

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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 pi-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...pi 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 H-1 NMR solution spectrum of [Cu(1)(3)][PF6] reveals hindered rotation of the phenyl rings of ligand.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Constable)
05 Faculty of Science > Departement Chemie > Chemie > Anorganische Chemie (Housecroft)
UniBasel Contributors:Constable, Edwin Charles and Housecroft, Catherine Elizabeth
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
e-ISSN:1466-8033
Note:Publication type according to Uni Basel Research Database: Journal article
Identification Number:
Last Modified:10 Apr 2017 14:21
Deposited On:14 Sep 2012 07:01

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