Reactions of Square-Planar d8 Pincer Complexes with Oxygen and Hydrogen

Wilson D. Bailey, Marie V. Parkes, Richard A. Kemp, Karen I. Goldberg

Research output: Chapter in Book/Report/Conference proceedingChapter

4 Scopus citations

Abstract

Reactions of palladium pincer complexes with molecular oxygen and hydrogen are described for homogeneous epoxidation catalysis. The proposed three-step catalytic cycle utilizes uncommon transformations that are tailored for a late-transition metal pincer complex: O2 insertion into a metal-hydride bond, O-atom transfer, and hydrogenolysis of the resulting metal hydroperoxide. Insertion reactions of O2 into palladium hydride bonds are described and a hydrogen atom abstraction (HAA) mechanism is proposed. Hydrogenolysis reactions of palladium hydroxide and alkoxide species are also described. Mechanistic investigations suggest a four-centered transition state between the palladium hydroxide and molecular hydrogen. Insights from both experimental and computational results are used to suggest optimal catalyst structure for the aforementioned transformations.

Original languageEnglish (US)
Title of host publicationPincer and Pincer-Type Complexes
Subtitle of host publicationApplications in Organic Synthesis and Catalysis
PublisherWiley-Blackwell
Pages281-298
Number of pages18
Volume9783527334421
ISBN (Electronic)9783527681303
ISBN (Print)9783527334421
DOIs
StatePublished - Aug 25 2014

Keywords

  • Epoxidation
  • Hydride
  • Hydrogen
  • Hydroxide
  • Oxygen
  • Palladium

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