Can I read Hydrocarbon Oxidation by β‐Halogenated Dioxoruthenium(VI) Porphyrin Complexes: Effect of Reduction Potential (Ru^VI/V^) and CH Bond‐Dissociation Energy on Rate Constants on EtoBox?

Hydrocarbon Oxidation by β‐Halogenated Dioxoruthenium(VI) Porphyrin Complexes: Effect of Reduction Potential (Ru^VI/V^) and CH Bond‐Dissociation Energy on Rate Constants by Chi‐Ming Che; Jun‐Long Zhang; Rui Zhang; Jie‐Sheng Huang; Tat‐Shing Lai; Wai‐Man Tsui; Xiang‐Ge Zhou; Zhong‐Yuan Zhou; Nianyong Zhu; Chi Kwong Chang is a scholarly article available to read on EtoBox.

What is Hydrocarbon Oxidation by β‐Halogenated Dioxoruthenium(VI) Porphyrin Complexes: Effect of Reduction Potential (Ru^VI/V^) and CH Bond‐Dissociation Energy on Rate Constants about?

## Abstract β‐Halogenated dioxoruthenium(VI) porphyrin complexes [Ru^VI^(F~28~‐tpp)O~2~] [F~28~‐tpp=2,3,7,8,12,13, 17,18‐octafluoro‐5,10,15,20‐tetrakis(pentafluorophenyl)porphyrinato(2−)] and [Ru^VI^(β‐Br~8~‐tmp)O~2~] [β‐Br~8~‐tmp=2,3,7,8,12,13,17,18‐octabromo‐5,10,15,20‐ tetrakis(2,4,6‐trimethylphenyl)porphyrinato(2−)] were prepared from reactions of [Ru^II^(por)(CO)] [por=porphyrinato(2−)] with __m__‐chloroperoxybenzoic acid in CH~2~Cl~2~. Reactions of [Ru^VI^(por)O~2~] with excess PPh~3~ in CH~2~Cl~2~ gave [Ru^II^(F~20~‐tpp)(PPh~3~)~2~] [F~20~‐tpp=5,10,15,20‐tetrakis(pentafluorophenyl)porphyrinato(2−)] and [Ru^II^(F~28~‐tpp)(PPh~3~)~2~]. The structures of [Ru^II^(por)(CO)(H~2~O)] and [Ru^II^(por)(PPh~3~)~2~] (por=F~20~‐tpp, F~28~‐tpp) were determined by X‐ray crystallography, revealing the effect of β‐fluorination of the porphyrin ligand on the coordination of axial ligands to ruthenium atom. The X‐ray crystal structure of [Ru^VI^(F~20~‐tpp)O~2~] shows a RuO bond length of 1.718(3) Å. Electrochemical reduction of [Ru^VI^(por)O~2~] (Ru^VI^ to Ru^V^) is irreversible or quasi‐reversible, with the __E__~p,c~(Ru^VI/V^) spanning −0.31 to −1.15 V versus Cp~2~Fe^+/0^. Kinetic studies w

Author

Chi‐Ming Che; Jun‐Long Zhang; Rui Zhang; Jie‐Sheng Huang; Tat‐Shing Lai; Wai‐Man Tsui; Xiang‐Ge Zhou; Zhong‐Yuan Zhou; Nianyong Zhu; Chi Kwong Chang

Publisher

John Wiley and Sons; Wiley (John Wiley & Sons); John Wiley & Sons Ltd.; Wiley (ISSN 0947-6539)

Published

2005

Language

EN