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High‐pressure mechanistic delineation based on activation volumes
Author(s) -
Jenner Gérard
Publication year - 2002
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.458
Subject(s) - chemistry , kinetics , kinetic energy , transition state theory , reaction mechanism , computational chemistry , mechanism (biology) , volume (thermodynamics) , hydrogen , high pressure , transition state , thermodynamics , reaction rate constant , organic chemistry , catalysis , philosophy , physics , epistemology , quantum mechanics
Abstract High‐pressure kinetics is a useful tool for the determination and the assessment of mechanisms in organic chemistry. The volume of activation Δ V * deduced from these kinetic measurements is an indicator of the position of the transition state. In addition, if accurately determined, Δ V * permits the detection of fine mechanistic effects such as alteration of mechanism according to substrates within the same reaction type, operation of secondary orbital interactions in Diels–Alder cycloadditions, angular hydrogen transfer in ene reactions, etc. Copyright © 2001 John Wiley & Sons, Ltd.