Substituent effects on cation-pi interactions: a quantitative study.
A synthetic supramolecular complex has been adapted to quantify cation-pi interactions in chloroform by using chemical double-mutant cycles. The interaction of a pyridinium cation with the pi-face of an aromatic ring is found to be very sensitive to the pi-electron density. Electron-donating substituents lead to a strong attractive interaction (-8 kJ/mol(-1)), but electron-withdrawing groups lead to a repulsive interaction (+2 kJ/mol(-1)).
Hunter
Christopher A
CA
Centre for Chemical Biology, Krebs Institute for Biomolecular Science, Department of Chemistry, University of Sheffield, Sheffield S3 7HF, United Kingdom. C.Hunter@Sheffield.ac.uk
Low
Caroline M R
CM
Rotger
Carmen
C
Vinter
Jeremy G
JG
Zonta
Cristiano
C
D002412:Cations; D002725:Chloroform / Q000737:chemistry; D004305:Dose-Response Relationship, Drug; D004583:Electrons; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D009154:Mutation; D011726:Pyridinium Compounds / Q000737:chemistry*; D013816:Thermodynamics
D002412:Cations; D011726:Pyridinium Compounds; D002725:Chloroform