On a way to new types of the polyfunctional and polytopic systems based on cage metal complexes: Cadmium-promoted nucleophilic substitution with low-active nucleophilic agents |
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Authors: | leg Varzatskii Yan Z Voloshin Sergey V Korobko Sergey V Shulga Roland Krmer Alexander S Belov Anna V Vologzhanina Yurii N Bubnov |
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Institution: | aVernadskii Institute of General and Inorganic Chemistry NANU, 03680 Kiev, Ukraine;bNesmeyanov Institute of Organoelement Compounds RAS, 119991 Moscow, Russia;cAnorganisch-Chemisches Institut, Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany |
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Abstract: | The nucleophilic substitution of the reactive halogen atoms of clathrochelate precursors with soft nucleophilic agents was promoted by cadmium(II) ion using various types of cadmium-containing compounds. Cadmium(II) activates the C–Hal bond both by the coordination of halogen substituents to this ion and the formation of anionic forms of a nucleophilic agent with cadmium amides, that increase the electron density on a reactive site of this agent. The cadmium-promoted substitution reactions of the reactive chlorine ribbed substituents in the di- and hexachlorine-containing clathrochelate precursors afforded the clathrochelate ribbed-functionalized derivatives of soft nucleophiles alcohols (including fluorinated ones) and aromatic amines (including the nucleophiles with electron-withdrawing substituents)] by efficient one-pot procedures in high yields under mild conditions with generated in situ low-basic cadmium(II) alcoholates and amides. The complexes obtained were characterized using elemental analysis, MALDI-TOF mass spectrometry, IR, UV–Vis, 57Fe Mössbauer, and NMR spectroscopies, and X-ray crystallography. The potential of cadmium-promoted reactions for synthesis of different types of organic and coordination compounds is discussed. |
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Keywords: | Iron complexes Clathrochelates Macrocyclic compounds Cadmium compounds Ligand reactivity |
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