Kang Runhua, Chen Kejuan, Yao Jiannian, Shaik Sason, Chen Hui
Beijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences , Beijing, 100190, China.
Inorg Chem. 2014 Jul 21;53(14):7130-6. doi: 10.1021/ic500008c. Epub 2014 Jun 26.
Ligand effects of some representative monomeric Ru-based water oxidation catalysts on the key O-O formation step are revealed in this work. Three effects, namely, cis-effect, net charge effect, and steric hindrance effect, are identified, which can exert sizable modulation on the O-O formation barriers for the two widely accepted O-O formation mechanisms of WNA (water nucleophilic attack) and I2M (direct coupling of two high-valent metal oxo units). The study demonstrates that, through the way of ligand design, there remains a large space for improving O-O bond formation reactivity.
本工作揭示了一些具有代表性的单体钌基水氧化催化剂在关键的O-O形成步骤中的配体效应。确定了三种效应，即顺式效应、净电荷效应和空间位阻效应，它们可以对WNA（水亲核攻击）和I2M（两个高价金属氧代单元的直接偶联）这两种广泛接受的O-O形成机制的O-O形成势垒产生相当大的调节作用。该研究表明，通过配体设计的方式，提高O-O键形成反应活性仍有很大空间。
