Selective surface decoration of corannulene.
The reaction of corannulene (C(20)H(10)) with 1,2-C(2)H(4)Hal(2) (Hal = Cl or Br) in the presence of AlCl(3) affords stable nonplanar carbocations C(20)H(10)CH(2)CH(2)Hal(+) (Hal = Cl (1) and Br (2)) with an -CH(2)CH(2)Hal moiety attached to the interior carbon atom of the bowl. In the analogous reaction with 1-bromo-2-chloroethane, the selective (up to 98%) abstraction of chloride is observed with the formation of cation 2. The molecular structures of bowl-shaped carbocations 1 and 2 crystallized as salts with AlCl(4)(-) counterions are revealed by single-crystal X-ray diffraction. The reaction of 2 with methanol or ethanol provides further decoration of the nonplanar polyarene upon the nucleophilic addition of alkoxy groups to the exterior carbon atom of the corannulene moiety. The (1)H NMR investigation of the corresponding products, C(20)H(10)(CH(2)CH(2)Br)(OCH(2)R) (R = H (3) and CH(3) (4)), shows the formation of intramolecular H···O and H···Br hydrogen bonds.
Department of Chemistry, University at Albany, State University of New York, 1400 Washington Avenue, Albany, New York 12222, USA.
Alexander V
AV
Zabula
Cristina
C
Dubceac
Alexander S
AS
Filatov
Marina A
MA
Petrukhina
D018360:Crystallography, X-Ray; D006846:Hydrocarbons, Halogenated / Q000138:chemical synthesis* / Q000737:chemistry; D006860:Hydrogen Bonding; D008958:Models, Molecular; D015394:Molecular Structure; D011084:Polycyclic Aromatic Hydrocarbons / Q000737:chemistry*; D013499:Surface Properties
D006846:Hydrocarbons, Halogenated; D011084:Polycyclic Aromatic Hydrocarbons; C434863:corannulene