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Capturing the Role of Explicit Solvent in the Dimerization of RuV(bda) Water Oxidation Catalysts
Shaoqi Zhan, Daniel Mårtensson, Miha Purg, Shina C. L. Kamerlin, and Mårten S. G. Ahlquist*

S. Zhan, D. Mårtensson, Dr. M. S. G. Ahlquist
Division of Theoretical Chemistry & Biology
School of Biotechnology, KTH Royal Institute of Technology 10691 Stockholm (Sweden)
DOI: 10.1002/anie.201701488
Angew. Chem. Int. Ed. 2017, 56, 1 – 5 

水の酸化の有効な触媒として7配位のRu錯体がある。この錯体はRu(V)=Oを形成したのちdimerとなって水の酸化を行うことが知られている。
本論文は初めてempirical valence bond (EVB)というシュミレーション方法を遷移金属錯体の触媒反応系に用いて、反応系における溶媒の効果を示している。

結論としてはRu=Oオキソの部分が疎水部であることが分かり、疎水性相互作用によりオキソ同士の向きが揃うことが一連の触媒サイクルの足がかりとなっていることを明らかにした。

触媒サイクルにおいての溶媒効果はあいかさんの修士論文で議論されていましたが、こういったシュミレーション方法を実験データを組み合わせて使えるのかなと思いました。


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