Isolation and structural characterization of a mainly ligand-based dimetallic radical.
A radical cation of ruthenium was isolated and structurally characterized. The EPR spectrum and theoretical calculations indicate that the spin density mainly resides on ligands. The X-ray structure shows that the change in metal-metal bond lengths is negligible upon one-electron oxidation. sp(3) C-H bond activation was observed during the reaction of the parent molecule with the trityl cation, which possibly occurs via an oxidative EC mechanism: a thermodynamically favorable electron-transfer to give the radical cation intermediate, followed by the hydrogen atom abstraction to afford a cationic tetramethylfulvene complex with formation of a metal-carbon bond.
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China. xpwang@nju.edu.cn.
Shuyu
S
Li
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China. xpwang@nju.edu.cn.
Xingyong
X
Wang
School of Chemistry and Chemical Engineering, Huaiyin Normal University, Huai'an 223300, China.
Zaichao
Z
Zhang
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China. xpwang@nju.edu.cn.
Yue
Y
Zhao
State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing 210093, China. xpwang@nju.edu.cn.
Xinping
X
Wang