One-electron oxidation of an organic molecule by B(C6F5)3; isolation and structures of stable non-para-substituted triarylamine cation radical and bis(triarylamine) dication diradicaloid.
The methylene-bridged triphenylamine 2 has been oxidized to planar radical cation 2(•+) by B(C6F5)3 or Ag(+). Further reaction of 2(•+)[Al(ORF)4](-) and 2 with trace amounts of silver salt resulted in dication 3(2+), providing a rare example of structurally characterized bis(triarylamine) "bipolarons". 3(2+) can be directly prepared by the reaction of 3 with 2 equiv of Ag(+). X-ray structural analysis together with theoretical calculation shows that 3(2+) has singlet diradical character and is analogous to Chichibabin's hydrocarbons.
State Key Laboratory of Coordination Chemistry and ‡Theoretical and Computational Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University , Nanjing 210093, China.
Xin
X
Zheng
Xingyong
X
Wang
Yunfan
Y
Qiu
Yuantao
Y
Li
Chenkun
C
Zhou
Yunxia
Y
Sui
Yizhi
Y
Li
Jing
J
Ma
Xinping
X
Wang