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Unusual Reaction Constant for Hydride Transfer from a Carbanion to 9‐Arylxanthyliums
Author(s) -
Liu Fengrui,
Zhu Xiaoqing
Publication year - 2014
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201403023
Subject(s) - chemistry , hydride , carbanion , reaction rate constant , kinetics , photochemistry , ion , reaction mechanism , chemical kinetics , inorganic chemistry , computational chemistry , medicinal chemistry , organic chemistry , catalysis , hydrogen , physics , quantum mechanics
The reaction constant ( ρ ) from the kinetics for hydride transfer from a carbanion (XH – ) to 9‐arylxanthylium ions (9‐GPhXn + ) in CH 3 CN was unusually negative. Thermodynamic analysis indicated that ρ for the simple hydride transfers (only involved with release and capture of a hydride anion) should be positive; this is in contrast to the kinetics results. Consequently, this reaction is not a simple hydride transfer. An “intermediate” was also found in the reaction system, the formation of which resulted in the unusual ρ .