Denysenko I. Functionalization of iron (II) clathrochelates by Cu– and Pd–promoted reactions

This dissertation is dedicated to developing methods of functionalization of halogen–substituted iron (II) clathrochelates with metal–promoted reactions and studying new types of macrobicyclic tris–dioximates. Seventeen new macrobicyclic clathrochelate iron (II) complexes have been synthesized and described. A systematic study of the conditions for trifluoroalkylation, perfluoroarylation, and partial exchange of reactive halogen atoms with Cu–promoted reactions has been conducted. Iron (II) clathrochelate complexes with trifluoromethyl and perfluoroaryl ribbed substituents directly linked to the clathrochelate backbone by a carbon–carbon bond have been synthesized for the first time. Selectivity of trifluoroalkylation reaction and partial exchange of halogen atoms has been determined to depend on the nature of the solvent and co–ligand which form the coordination reactive organometallic compound. The efficiency of using copper organometallic compound CuC6F5 for modification of electron–deficient iron (II) complex compounds has been demonstrated. A method for synthesizing mixed–halide iron (II) clathrochelate based on copper–promoted reactions of halogen atom exchange has been examined. Pd– and Pd/Cu–promoted reactions of arylation (Suzuki reaction) and ethynylation (Sonogashira reaction) of halogen–substituted iron (II) clathrochelates have been studied, reaction paths have been determined, and conditions for carbon–carbon bond formation between clathrochelate and carbanion synthons have been determined.