Oxygen‐Promoted CH Bond Activation at Palladium1. (9th May 2014)

• Record Type: Journal Article
• Authors: Scheuermann, Margaret L.; Boyce, David W.; Grice, Kyle A.; Kaminsky, Werner; Stoll, Stefan; Tolman, William B.; Swang, Ole; Goldberg, Karen I.
• Is Part Of: Angewandte Chemie. Volume 126:Number 25(2014)
• Page Start: 6610
• Page End: 6613
• Publication Date: 2014-05-09
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201402484
• Languages: English
• ISSNs: 0044-8249

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>[Pd(P(Ar)(<italic>t</italic>Bu)₂)₂] (<bold>1</bold>, 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 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.</p> </abstract>