Investigation of long-distance intramolecular electronic interactions and reactivity of mono- and binuclear aminocarbene complexes using electrochemical methods

Abstract:
Mono- and binuclear aminocarbene complexes belong to molecules with multiple redox centres. Their intramolecular (long-distance) electronic interactions and their mutual influence can be investigated using interpretation of electrochemical data. This enables to formulate general rules for design of new catalysts. For this reason a series of p-dicarbonyl benzene model compounds and phenylene-bridged binuclear aminocarbene complexes will be synthesized and studied. Attention will be paid also to axially chiral compounds with high sterical hindrance between the o-substituted phenyl ring on the carbene carbon atom and dimethylamino group. Detailed mechanism of the electrochemical and electrochemically initiated processes will be determined, with special attention to reduction because of the importance of reduced electrophilic Fischer-type carbene complexes in organic synthesis and catalysis. All experiments will be compared and correlated with MO calculations.