Copper(II) template synthesis of a new N2S2-donor macrocycle incorporating a pendent pyridyl substituent |
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Authors: | Cindy Mora Young Hoon Lee Jack K. Clegg Leonard F. Lindoy Hong In Lee Woo Taik Lim Yang Kim |
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Affiliation: | 1. Department of Chemistry and Advanced Materials, Kosin University, 149-1, Dongsam-dong, Yeongdo-gu, Busan, 606-701, South Korea 2. School of Chemistry, The University of Sydney, Sydney, NSW, 2006, Australia 3. Department of Chemistry, Kyungpook National University, Daegu, 702-701, South Korea 4. Department of Applied Chemistry, Andong National University, Kyungpook, South Korea
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Abstract: | The synthesis of the new potentially pentadentate ligand, 2,2??-(2-methyl-2-(pyridin-2-yl)propane-1,3-diyl)bis(sulfanediyl)diethanamine (L 1 ), containing two thioether sulfurs, two ?CNH2 amines and a pyridyl nitrogen heteroatom is described. Reaction of L 1 with copper(II) chloride and addition of hexafluorophosphate anion has led to isolation of the mixed anion complex Cu2(L 1 )2Cl(PF6)3. The synthesis and X-ray structure of cobalt(III) species, [Co(L 1 )Cl](PF6)2, is also reported. In situ reaction of L 1 with copper(II) as a metal template in the presence of formaldehyde and the carbon acid nitroethane together with triethylamine (as base) led to macrocycle ring closure to yield [Cu(L 2 )Cl]PF6 (where L 2 = 6,13-dimethyl-6-nitro-13-(pyridin-2-yl)-1,11-dithia-4,8-diazacyclotetradecane) whose X-ray structure shows that the copper centre has a distorted square pyramidal coordination geometry being bound by both ?CNH2 nitrogens and both sulfurs of L 2 while the pyridyl nitrogen remains uncoordinated. |
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