Hydrogen-Bonded Complex of the Simplest Phosphine Oxide with Water
Bifeng Zhu, Ziting Ma, Can Zhou, Xianxu Chu, Fang Fang, Zichun Zhu, Junjie JiangAbstract
The simplest phosphine oxide OPH3, a key intermediate in the oxidation of phosphine PH3, has been of long-term interest in theoretical and experimental chemistry. By UV photolysis (254 nm) of an atmospherically important complex between PH3 and hydrogen peroxide H2O2, the elusive OPH3 has been generated as a hydrogen-bonded water complex in cryogenic N2 and Ar matrices at 10 K. The spectroscopic identification of this complex is supported by D-isotope labeling and quantum-chemical calculations. Calculations on the potential energy profile for the rearrangement from PH3···H2O2 to OPH3···H2O demonstrate that the concerted mechanism is energetically preferred at the CCSD(T)-F12a/aug-cc-pVTZ//B3LYP/6–311++G(3df,3pd) level of theory. The formation of the molecular complex between PH3 and H2O2 and its subsequent photoisomerization to OPH3···H2O might be of interest for understanding the networks of the atmospheric phosphorus chemistry.