Extremely reactive carbenes: electrophiles and nucleophiles†. (26th April 2016)

• Record Type: Journal Article
• Authors: Moss, Robert A.; Wang, Lei; Cang, Hui; Krogh‐Jespersen, Karsten; Abe, Manabu; Sheridan, Robert S.
• Is Part Of: Journal of physical organic chemistry. Volume 30:Number 4(2017)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2016-04-26
• Subjects: activation parameters -- calculations -- carbenes -- HOMO/LUMO energies -- kinetics; Chemistry, Physical organic -- Periodicals; 547.1
• DOI: 10.1002/poc.3555
• Languages: English
• ISSNs: 0894-3230

Abstract

Abstract : We describe the intermolecular reactivity toward alkenes of several extremely reactive carbenes as determined by experimental and computational methods. Among the examined species are the electrophiles trifluoromethylchlorocarbene and ( N ‐methyl‐3‐pyridinium)chlorocarbene and the nucleophiles adamantanylidene and dimethylcarbene. Phenomena discussed include negative activation energies for addition reactions and apparent compensation between the enthalpies and entropies of activation. Copyright © 2016 John Wiley & Sons, Ltd. Abstract : We analyze trends in the measured activation parameters for the additions of representative electrophilic and nucleophilic carbenes to alkenes.