ja402492u_si_004.cif (70.66 kB)

Stable Tetraaryldiphosphine Radical Cation and Dication

Download (70.66 kB)
posted on 17.04.2013, 00:00 by Xiaobo Pan, Yuanting Su, Xiaoyu Chen, Yue Zhao, Yizhi Li, Jinglin Zuo, Xinping Wang
Salts containing tetraaryldiphosphine radical cation 1•+ and dication 12+ have been isolated and structurally characterized. Radical 1•+ has a relaxed pyramidal geometry, while dication 12+ prefers a planar, olefin-like geometry with a two-electron π bond. The alteration of the geometries of the tetraaryldiphosphine upon oxidation is rationalized by the nature of the bonding. The EPR spectrum showed that the spin density of radical 1•+ is mainly localized on phosphorus atoms, which is supported by theoretical calculation.