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Mechanisms and Activity of 1‐Phenylethanol Dehydrogenation Catalyzed by Bifunctional NHC‐Ir III Complex
Author(s) -
Wang Qiong,
Guo CaiHong,
Zhang Xiang,
Zhu Mi,
Jiao Haijun,
Wu HaiShun
Publication year - 2019
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.201900377
Subject(s) - chemistry , dehydrogenation , acetophenone , bifunctional , catalysis , carbene , kinetic isotope effect , photochemistry , solvation , medicinal chemistry , solvent , organic chemistry , deuterium , physics , quantum mechanics
Acceptorless dehydrogenation of 1‐phenylethanol to acetophenone catalyzed by OH‐functionalized N‐heterocyclic carbene Cp*Ir(NHC) complexes under base‐free condition as well as under the promotion of protic co‐solvent t BuOH were investigated using density functional theory including solvation and van der Waals dispersion corrections. The first step is the 1‐phenylethanol dehydrogenation, which is more favored via an inner‐sphere over an outer‐sphere mechanism. The second step is H 2 formation from Ir–H and O–H functionalities, which is the rate‐determining step, in agreement with the observed kinetic isotopic effect. The protic co‐solvent and 1‐phenylethanol act as a shuttle for proton transfer for the formation of H 2 .