Synthesis and stereochemistry of cobalt(III) complexes containing 2-thiocytocine and derivatives
- 1 January 1993
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 11,p. 1651-1655
- https://doi.org/10.1039/dt9930001651
Abstract
Three series of mixed-ligand cobalt(III) complexes containing four-membered N,S chelates [CoLn(en)3–n](3–n)+[n= 1 or 2; HL = 2-thiocytocine (4-aminopyrimidine-2-thione, Hapymt), 4,6-diaminopyrimidine-2-thione (4,6-Hdapymt) or 2,4-diaminopyrimidine-6-thione (2,4-Hdapymt); en = ethane-1,2-diamine] have been prepared photochemically and/or thermally and characterized by elemental analysis, UV/VIS absorption, and 1H and 13C NMR spectra. The crystal structure of [Co(apymt)(en)2][ClO4]2 was determined from 1897 observed reflections to R= 0.048 (R′= 0.053): space group Pbca(orthorhombic) with a= 11.849(7), b= 27.551(8), c= 11.201(3)Å and Z= 8. The apymt ligand co-ordinates through the N1 and S2 donors and the complex adopts a remote linkage form where the C4 amino group is distant from the en chelate rings. A new type of intramolecular hydrogen bond between the co-ordinated sulfur atom of one dapymt ligand and one of the amino groups of the other dapymt ligand was found in trans-(S)-[Co(4,6-dapymt)(en)2]+ and trans-(S)-[Co(2,4-dapymt)(en)2]+, which is responsible for their relatively high formation yield.Keywords
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