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Is copper(I) really soft? probing the hardness of Cu(I) with pyridinecarboxaldehyde ligands

Saravanabharathi, D and Nethaji, M and Samuelson, AG (2002) Is copper(I) really soft? probing the hardness of Cu(I) with pyridinecarboxaldehyde ligands. In: Journal of Chemical Sciences, 114 (4). pp. 347-356.

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Abstract

Cu(I) complexes of formula Cu(PPh3)(2)LClO4 [L = 2 or 3 pyridine carboxaldehyde] are synthesised and characterised to explore the coordination of an aldehyde, a hard and neutral oxygen donor to a soft Cu(1) centre. The structural and spectroscopic results illustrate that only in 2- pyridinecarboxaldehyde, the C=O group coordinates to soft Cu(l) centres due to a favourable chelate effect, while in 3- pyridinecarboxaldehyde, it remains uncoordinated. Upon chelation via N and O donors, 2-pyridinecarboxaldchyde resembles bipyridine or phenanthroline in terms of its bite angle and spectroscopic features. Such chelation can be easily challenged with coordinating anions like bromide, or more basic pyridines. A drastic change in the MLCT absorption signals the decomplexation of the C=O group. The observed results point out that the Cu(I) centre can readily exchange the hard O donor for softer ligands.

Item Type: Journal Article
Additional Information: Copyright for this article belongs to Indian Academy of Sciences.
Keywords: Cu(I) complexes;pyridinecarboxaldehyde;HSAB;competition reactions;chelate effect
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 22 Sep 2004
Last Modified: 19 Sep 2010 04:16
URI: http://eprints.iisc.ernet.in/id/eprint/1996

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