C−H Activation by an Iron-Nitrido Bis-Pocket Porphyrin Species
Dr. Hai-Xu Wang
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorDr. Liangliang Wu
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorBin Zheng
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorDr. Lili Du
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorDr. Wai-Pong To
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorCheng-Hoi Ko
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorCorresponding Author
Prof. Dr. David Lee Phillips
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorCorresponding Author
Prof. Dr. Chi-Ming Che
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
HKU Shenzhen Institute of Research & Innovation, Shenzhen, China
Search for more papers by this authorDr. Hai-Xu Wang
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorDr. Liangliang Wu
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorBin Zheng
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorDr. Lili Du
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorDr. Wai-Pong To
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorCheng-Hoi Ko
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorCorresponding Author
Prof. Dr. David Lee Phillips
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
Search for more papers by this authorCorresponding Author
Prof. Dr. Chi-Ming Che
State Key Laboratory of Synthetic Chemistry and Department of Chemistry, The University of Hong Kong, Pokfulam Road, Hong Kong, China
HKU Shenzhen Institute of Research & Innovation, Shenzhen, China
Search for more papers by this authorDedicated to Professor Harry B. Gray on the occasion of his 85th birthday
Abstract
High-valent iron-nitrido species are nitrogen analogues of iron-oxo species which are versatile reagents for C−H oxidation. Nonetheless, C−H activation by iron-nitrido species has been scarcely explored, as this is often hampered by their instability and short lifetime in solutions. Herein, the hydrogen atom transfer (HAT) reactivity of an Fe porphyrin nitrido species (2 c) toward C−H substrates was studied in solutions at room temperature, which was achieved by nanosecond laser flash photolysis (LFP) of its FeIII-azido precursor (1 c) supported by a bulky bis-pocket porphyrin ligand. C−H bonds with bond dissociation enthalpies (BDEs) of up to ≈84 kcal mol−1 could be activated, and the second-order rate constants (k2) are on the order of 102–104 s−1 m−1. The Fe-amido product formed after HAT could further release ammonia upon protonation.
Conflict of interest
The authors declare no conflict of interest.
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