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Oxygen‐Promoted CH Bond Activation at Palladium
Author(s) -
Scheuermann Margaret L.,
Boyce David W.,
Grice Kyle A.,
Kaminsky Werner,
Stoll Stefan,
Tolman William B.,
Swang Ole,
Goldberg Karen I.
Publication year - 2014
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.201402484
Subject(s) - palladium , chemistry , catalysis , oxygen , phosphine , bond cleavage , medicinal chemistry , ring (chemistry) , oxygen atom , hydroxide , photochemistry , cleavage (geology) , stereochemistry , inorganic chemistry , molecule , organic chemistry , materials science , fracture (geology) , composite material
[Pd(P(Ar)( t Bu) 2 ) 2 ] ( 1 , Ar=naphthyl) reacts with molecular oxygen to form Pd II hydroxide dimers in which the naphthyl ring is cyclometalated and one equivalent of phosphine per palladium atom is released. This reaction involves the cleavage of both CH and OO bonds, two transformations central to catalytic aerobic oxidizations of hydrocarbons. Observations at low temperature suggest the initial formation of a superoxo complex, which then generates a peroxo complex prior to the CH activation step. A transition state for energetically viable CH activation across a Pdperoxo bond was located computationally.