Oxygen-Promoted CH Bond Activation at Palladium

[Pd(P(Ar)(tBu)2)2] (1, Ar=naphthyl) reacts with molecular oxygen to form PdII 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 CH and OO bonds, two transformations central to ca...

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Bibliographic Details
Published in:Angewandte Chemie 2014-06, Vol.126 (25), p.6610-6613
Main Authors: Scheuermann, Margaret L., Boyce, David W., Grice, Kyle A., Kaminsky, Werner, Stoll, Stefan, Tolman, William B., Swang, Ole, Goldberg, Karen I.
Format: Article
Language:English
Subjects:
Activation
Bonding
C-H-Aktivierung
Chemistry
Cleavage
Dimers
Equivalence
Hydrocarbons
Hydroxylierungen
Low temperature
Oxygen
Palladium
Peroxo
Phosphine
Phosphines
Superoxo
Transformations
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Summary:[Pd(P(Ar)(tBu)2)2] (1, Ar=naphthyl) reacts with molecular oxygen to form PdII 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 CH and OO 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 CH activation step. A transition state for energetically viable CH activation across a Pdperoxo bond was located computationally. Peroxo greift an: [Pd(P(Ar)(tBu)2)2] (Ar=Naphthyl) reagiert mit molekularem Sauerstoff unter C‐H‐ und O‐O‐Bindungsspaltung. Bei tiefen Temperaturen wird die anfängliche Bildung eines Superoxo‐Komplexes beobachtet, der vor dem C‐H‐Aktivierungsschritt in einen Peroxo‐Komplex übergeht. Eine energetisch plausible C‐H‐Aktivierung durch die Pd‐Peroxo‐Bindung wurde rechnerisch identifiziert.
ISSN:0044-8249
1521-3757
DOI:10.1002/ange.201402484