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Mechanistic Studies on Photoinduced Catalytic Olefin Migration Reactions at the Pd(II) Centers of a Porous Crystal, Metal‐Macrocycle Framework
Author(s) -
Yonezawa Hirotaka,
Shiraogawa Takafumi,
Han Mengying,
Tashiro Shohei,
Ehara Masahiro,
Shionoya Mitsuhiko
Publication year - 2021
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.202001306
Subject(s) - olefin fiber , catalysis , chemistry , metal , crystal (programming language) , alkyl , oniom , photochemistry , porosity , organic chemistry , computer science , programming language
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 Cl 2 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.