Highly Regioselective Alkylation of Hexabenzocoronenes: Fundamental Insights into the Covalent Chemistry of Graphene. Issue 40 (23rd August 2017)

• Record Type: Journal Article
• Authors: Holzwarth, Johannes; Amsharov, Konstantin Yu.; Sharapa, Dmitry I.; Reger, David; Roshchyna, Kateryna; Lungerich, Dominik; Jux, Norbert; Hauke, Frank; Clark, Timothy; Hirsch, Andreas
• Is Part Of: Angewandte Chemie international edition. Volume 56:Issue 40(2017)
• Page Start: 12184
• Page End: 12190
• Publication Date: 2017-08-23
• Subjects: alkylation -- density-functional calculations -- graphene -- radicals -- reaction mechanisms; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201706437
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Hexa‐ peri ‐hexabenzocoronides (HBC) was successfully used as a model system for investigating the complex mechanism of the reductive functionalization of graphene. The well‐defined molecular HBC system enabled deeper insights into the mechanism of the alkylation of reductively activated nanographenes. The separation and complete characterization of alkylation products clearly demonstrate that nanographene functionalization proceeds with exceptionally high regio‐ and stereoselectivities on the HBC scaffold. Experimental and theoretical studies lead to the conclusion that the intact basal graphene plane is chemically inert and addend binding can only take place at either preexisting defects or close to the periphery. Abstract : In 'plane' view : Experimental and theoretical studies lead to the conclusion that the intact basal graphene plane is chemically inert and addend binding can only take place at either preexisting defects or close to the periphery. The free movement of alkyl radicals (see picture) in the neutral van der Waals complex HBC‐R . is a key step of the entire sequence. HBC=hexa‐ peri ‐hexabenzocoronide.