Stereoselectivity in the metal-controlled synthesis of the alkylated thiosemicarbazones
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COCU, Maria, GRĂDINARU, Julieta, MALINOVSKII, Stanislav, REVENKO, M., GDANIEC, Maria. Stereoselectivity in the metal-controlled synthesis of the alkylated thiosemicarbazones. In: Physical Methods in Coordination and Supramolecular Chemistry, 27 septembrie - 1 octombrie 2006, Chişinău. Chisinau, Republic of Moldova: 2006, XVII, p. 114. ISBN 978-9975-62-066-6.
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Physical Methods in Coordination and Supramolecular Chemistry
XVII, 2006
Conferința "The XV-th International Conference Physical Methods in Coordination and Supramolecular Chemistry : The XVII-th Reading in memory of Acad. A.Ablov"
Chişinău, Moldova, 27 septembrie - 1 octombrie 2006

Stereoselectivity in the metal-controlled synthesis of the alkylated thiosemicarbazones


Pag. 114-114

Cocu Maria1, Grădinaru Julieta1, Malinovskii Stanislav1, Revenko M.1, Gdaniec Maria2
 
1 Institute of Chemistry,
2 Adam Mickiewicz University in Poznan
 
 
Disponibil în IBN: 9 iunie 2020


Rezumat

The template condensation of the thiosemicarbazide with carbonylic compounds in the presence of metal ions is favored by the formation of the stable complexes with the resulting ligand. The last one may be usually a thiosemicarbazone, or, in some cases, a more sophisticated template assembled chemical edifice. The role of the metal ion in these reactions is very multilateral. The formation of the thiosemicarbazone species is directed by the metal ion to prevent the cyclization of the ligsons, or to achieve the more convenient coordination mode of the newly appeared ligand to the taken metal ion, ensuring its thermodynamic and stereochemical needs. We discuss in this presentation the role of the metal ion in stabilization of some isomer forms of 2,6-dicarbonylpyridine bis-(S-methyl-isothiosemicarbazones). The interaction of the 2,6-diacetyl- or 2,6-diformyl- pyridine with S-methylthiosemicarbazide in the presence of Mn(II) or Ni(II) gives rise to the formation of the complexes containing as a ligand the respective bis-(Smethylisothiosemicarbazones) (H2L). The difference occurs only in the geometry of the thiosemicarbazide fragments. In the Mn(II) complex the newly formed ligand adopts E-configurations for the both azometinic bonds and cis-orientation of the marginal nitrogen atoms. The bis-(S-methylisothiosemicarbazone) is a pentadentate N5 ligand [1]. In the nickel complexes, one of the thiosemicarbazide fragments has Z-configuration and a trans-orientation of the marginal nitrogen atoms. Such geometry does not allow the coordination of the N(1) atom and creates new convenient conditions for the coordination of the atom N(2) (see fig.) [2]. H2L acts in this complex as a tetradentate N4 ligand. The role of the metal ions peculiarities in the selective orientation of the thiosemicarbazide fragment in this metalcontrolled condensation is discussed.