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

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Abstract

Cu(I) complexes of formula Cu(PPh3)2LClO4 [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(I) centre. The structural and spectroscopic results illustrate that only in 2-pyridinecarboxaldehyde, the ‘C=O’ group coordinates to soft Cu(I) centres due to a favourable chelate effect, while in 3-pyridinecarboxaldehyde, it remains uncoordinated. Upon chelation via N and O donors, 2-pyridinecarboxaldehyde 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.

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Authors and Affiliations

  1. Department of Inorganic and Physical Chemistry, Indian Institute of Science, 560 012, Bangalore, India

    D. Saravanabharathi, M. Nethaji & A. G. Samuelson

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  1. D. Saravanabharathi
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  2. M. Nethaji
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  3. A. G. Samuelson
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Correspondence to A. G. Samuelson.

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Saravanabharathi, D., Nethaji, M. & Samuelson, A.G. Is copper(I) really soft? Probing the hardness of Cu(I) with pyridinecarboxaldehyde ligands. J Chem Sci 114, 347–356 (2002). https://doi.org/10.1007/BF02703825

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