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Effect of H-bonding on the ambivalence of SCN- towards copper(II)

Drew, M. G. B., Das, D., De, S. and Datta, D. (2009) Effect of H-bonding on the ambivalence of SCN- towards copper(II). Inorganica Chimica Acta, 362 (5). pp. 1501-1505. ISSN 0020-1693

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To link to this item DOI: 10.1016/j.ica.2008.07.007


Condensations of 2-(2-aminoethyl)pyridine with 4-methylimidazole-5-carboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde generate the tridentate N donor ligands L and L' respectively. Reactions of Cu(NCS)(2) with L and L' yield respectively CuL(SCN)(NCS) (1) containing a CuN4S core and CuL'(NCS)(2) (2) having a CuN5 core. Both the cores are square pyramidal with SCN bound in 1 at the axial position through the S end. This differential behaviour of SCN in the two complexes despite the ligands being very similar, is investigated by DFT calculations at the B3LYP/TZV level. It is found that DFT calculations predict isolation of the Cu(ligand)(NCS)(2) species for both the ligands L and L'. Presence of an offsetting intermolecular H-bonding between the N atom of the thiocyanate and the N-H proton of the ligand L of an adjacent molecule makes the binding of SCN via the S end feasible in 1 resulting in the H-bonded-dimer Cu2L2(SCN)(2)(NCS)(2). The strength of the H-bond is estimated as 27.1 kJ mol (1) from the DFT calculations. The question of such H-bonding does not arise with L' as it lacks in a similar H atom. Dimeric 1 represents a case of two non-interacting spins. (C) 2008 Elsevier B. V. All rights reserved.

Item Type:Article
Divisions:Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11203
Uncontrolled Keywords:Copper(II), N ligands, structural isomers, H-bond, thiocyanate, DFT, HYDROXIDE COMPLEXES, STABILITY, NANOTUBES, CHEMISTRY, MODEL, STATE, ZINC

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