Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

Yunling Pan; Miaomiao Zhou; Rui Wang; Dan Song; Shek-Man Yiu; Jianhui Xie; Kai-Chung Lau; Tai-Chu Lau; Yingying Liu

doi:10.1021/acs.inorgchem.3c00417

Structure and Reactivity of a Seven-Coordinate Ruthenium Iodosylbenzene Complex

Inorg Chem. 2023 May 22;62(20):7772-7778. doi: 10.1021/acs.inorgchem.3c00417. Epub 2023 May 5.

Authors

Yunling Pan^{1

2}, Miaomiao Zhou³, Rui Wang¹, Dan Song^{1

2}, Shek-Man Yiu³, Jianhui Xie², Kai-Chung Lau³, Tai-Chu Lau^{3

4}, Yingying Liu¹

Affiliations

¹ Institute of Intelligent Machines, Hefei Institutes of Physical Science, Chinese Academy of Sciences, Hefei 230031, P. R. China.
² Anhui Province Key Laboratory of Advanced Catalytic Materials and Reaction Engineering, School of Chemistry and Chemical Engineering, Hefei University of Technology, Hefei 230009, P. R. China.
³ Department of Chemistry, City University of Hong Kong, Kowloon Tong 999077, Hong Kong, P. R. China.
⁴ Research Center for Eco-environmental Engineering, Dongguan University of Technology, Dongguan 523808, P. R. China.

PMID: 37146252
DOI: 10.1021/acs.inorgchem.3c00417

Abstract

Seven-coordinate (CN7) ruthenium-oxo species have attracted much attention as highly reactive intermediates in both organic and water oxidation. Apart from metal-oxo, other metal-oxidant adducts, such as metal-iodosylarenes, have also recently emerged as active oxidants. We reported herein the first example of a CN7 Ru-iodosylbenzene complex, [Ru^IV(bdpm)(pic)₂(O)I(Cl)Ph]⁺ (H₂bdpm = [2,2'-bipyridine]-6,6'-diylbis(diphenylmethanol); pic = 4-picoline). The X-ray crystal structure of this complex shows that it adopts a distorted pentagonal bipyramidal geometry with Ru-O(I) and O-I distances of 2.0451(39) and 1.9946(40) Å, respectively. This complex is highly reactive, and it readily undergoes O-atom transfer (OAT) and C-H bond activation reactions with various organic substrates. This work should provide insights for the development of new highly reactive oxidizing agents based on CN7 geometry.