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First X‐Ray Structure Analyses of Rhodium(III) η 1 ‐Allyl Complexes and a Mechanism for Allylic Isomerization Reactions
Author(s) -
Wucher Barbara,
Moser Michael,
Schumacher Stephanie A.,
Rominger Frank,
Kunz Doris
Publication year - 2009
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.200805899
Subject(s) - isomerization , rhodium , regioselectivity , allylic rearrangement , chemistry , substituent , tsuji–trost reaction , catalysis , x ray , metal , medicinal chemistry , stereochemistry , photochemistry , organic chemistry , physics , quantum mechanics
Metal‐to‐metal allyl transfer : Using the first structurally characterized rhodium η 1 ‐allyl complexes it is shown that the σ‐bound allyl substituent can be transferred from the Rh III complex to a Rh I complex in a fast equilibrium. This process may account for the decrease in regioselectivity observed in allylic alkylation reactions in which complex 1 is used as a catalyst.