Mechanistic Studies on Photoinduced Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal‐Macrocycle Framework. Issue 3 (22nd December 2020)

• Record Type: Journal Article
• Authors: Yonezawa, Hirotaka; Shiraogawa, Takafumi; Han, Mengying; Tashiro, Shohei; Ehara, Masahiro; Shionoya, Mitsuhiko
• Is Part Of: Chemistry, an Asian journal. Volume 16:Issue 3(2021)
• Page Start: 202
• Page End: 206
• Publication Date: 2020-12-22
• Subjects: mechanism -- metallacycles -- olefin migration -- palladium -- photoactivation; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/asia.202001306
• Languages: English
• ISSNs: 1861-4728

Abstract

Abstract: Porous crystals with well‐defined active metal centers on the pore surface have high potential as heterogeneous metal catalysts. We have recently demonstrated that a porous molecular crystal, metal‐macrocycle framework (MMF), catalyzes olefin migration reactions by photoactivation of its Pd II Cl2 moieties exposed on the crystalline channel surface. Herein we report a mechanistic study of the photoinduced olefin migration reactions at the Pd II active centers of MMF. Several experiments, including a deuterium scrambling study, revealed that olefin migration is catalyzed via an alkyl mechanism by in situ generated Pd−H species on the channel surface during photoirradiation. This proposed mechanism was further supported by DFT and ONIOM calculations. Abstract : A mechanistic study of photoinduced olefin migration reactions at the Pd II active centers of a porous molecular crystal, metal‐macrocycle framework (MMF) is reported. Several experiments, including a deuterium scrambling study, and theoretical calculations revealed that olefin migration is catalyzed via an alkyl mechanism by in situ generated Pd−H species on the channel surface during photoirradiation.