An Isolable Diphosphene Radical Cation Stabilized by Three‐Center Three‐Electron π‐Bonding with Chromium: End‐On versus Side‐On Coordination |
| |
| Authors: | Wenqing Wang Cong‐Qiao Xu Yong Fang Yue Zhao Prof Jun Li Prof Xinping Wang |
| |
| Institution: | 1. State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Collaborative Innovation Center of Advanced Microstructures, Nanjing University, Nanjing, China;2. Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing, China |
| |
| Abstract: | Two salts ( 2 and 4 ) containing the radical cations of complexed diphosphenes have been isolated and characterized by electron paramagnetic resonance (EPR) spectroscopy, IR spectroscopy, and single‐crystal X‐ray diffraction. The P?P bond is coordinated to the Cr center either in an end‐on (in 2 ) or a side‐on (in 4 ) fashion. The spin density of the radical is delocalized over the Cr atom and the two P atoms in 2 whereas the unpaired electron is mainly localized on the Cr atom in 4 . This work provides the first example of a complexed diphosphene radical ( 2 ) featuring novel three‐center three‐electron (3c‐3e) π‐bonding in the Cr‐P‐P unit, and the first example of a 17 e Cr radical with a side‐on π‐bonded ligand ( 4 ). |
| |
| Keywords: | diphosphenes EPR spectroscopy phosphorus radical cations X-ray diffraction |
|
|
