Kinetic and equilibrium lithium acidities of arenes: theory and experiment.
Kinetic acidities of arenes, ArH, measured some time ago by hydrogen isotope exchange kinetics with lithium cyclohexylamide (LiCHA) in cyclohexylamine (CHA) show a wide range of reactivities that involve several electronic mechanisms. These experimental reactivities give an excellent Brønsted correlation with equilibrium lithium ion pair acidities (pK(Li)) derived as shown recently from computations of ArLi.2E (E = dimethyl ether). The various electronic mechanisms are well modeled by ab initio HF calculations with modest basis sets. Additional calculations using NH(3) as a model for CHA further characterize the TS of the exchange reactions. The slopes of Brønsted correlations of ion pair systems can vary depending on the nature of the ion pairs.
Streitwieser
Andrew
A
Department of Chemistry, University of California-Berkeley, Berkeley, California 94720-1460, USA. astreit@berkeley.edu
Shah
Kamesh
K
Reyes
Julius R
JR
Zhang
Xingyue
X
Davis
Nicole R
NR
Wu
Eric C
EC
D000143:Acids / Q000737:chemistry*; D000641:Ammonia / Q000737:chemistry; D003514:Cyclohexylamines / Q000737:chemistry*; D007700:Kinetics; D008094:Lithium / Q000737:chemistry*; D056004:Molecular Dynamics Simulation; D015394:Molecular Structure; D011789:Quantum Theory
D000143:Acids; D003514:Cyclohexylamines; D000641:Ammonia; D008094:Lithium