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Promoting Proton Transfer and Stabilizing Intermediates in Catalytic Water Oxidation via Hydrophobic Outer Sphere Interactions
Author(s) -
Liu Tianqi,
Li Ge,
Shen Nannan,
Wang Linqin,
Timmer Brian J. J.,
Kravchenko Alexander,
Zhou Shengyang,
Gao Ying,
Yang Yi,
Yang Hao,
Xu Bo,
Zhang Biaobiao,
Ahlquist Mårten S. G.,
Sun Licheng
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202104562
Subject(s) - catalysis , outer sphere electron transfer , chemistry , proton , coordination sphere , inner sphere electron transfer , photochemistry , kinetics , chemical engineering , molecule , organic chemistry , ion , physics , quantum mechanics , engineering
The outer coordination sphere of metalloenzyme often plays an important role in its high catalytic activity, however, this principle is rarely considered in the design of man‐made molecular catalysts. Herein, four Ru‐bda (bda=2,2′‐bipyridine‐6,6′‐dicarboxylate) based molecular water oxidation catalysts with well‐defined outer spheres are designed and synthesized. Experimental and theoretical studies showed that the hydrophobic environment around the Ru center could lead to thermodynamic stabilization of the high‐valent intermediates and kinetic acceleration of the proton transfer process during catalytic water oxidation. By this outer sphere stabilization, a 6‐fold rate increase for water oxidation catalysis has been achieved.