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A case of four-coordinate silver(I) adopting a high energy planar geometry. Experiment and theory

Chowdhury, S. , Drew, M.G.B. and Datta, D. (2003) A case of four-coordinate silver(I) adopting a high energy planar geometry. Experiment and theory. New Journal of Chemistry, 27 (5). pp. 831-835. ISSN 1144-0546

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To link to this item DOI: 10.1039/b211898j

Abstract/Summary

The ligands PhL and MeL are obtained by condensing 2-formylpyridine with benzil dihydrazone and diacetyl dihydrazone, respectively, in 2: 1 molar proportion. With silver( I), PhL yields a double-stranded dinuclear cationic helicate 1 in which the metal is tetrahedral but MeL gives a cationic one-dimensional polymeric complex 2 where silver( I) is distorted square planar and the ligand backbone is nearly planar. In both complexes, metal: ligand ratio is 1: 1. Ab initio calculations on the ligands at the HF/6-31+G* level reveal that while PhL strongly prefers a helical conformation, MeL has a natural inclination to remain in a planar conformation. Density functional theory calculations on model silver( I) complexes show that formation of the linear polymer in the case of MeL is also an important factor in imposing the planar geometry of Ag(I) in 2.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:11138
Uncontrolled Keywords:METAL, CHROMOPHORE, COPPER(I), COMPLEXES, HELICATE

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