Splitting Molecular Oxygen en Route to a Stable Molecule Containing Diphosphorus Tetroxide

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• 作者：Yuzhong Wang ; Yaoming Xie ; Pingrong Wei ; Henry F. Schaefer ; III ; Paul von R. Schleyer ; Gregory H. Robinson
• 刊名：Journal of the American Chemical Society
• 出版年：2013
• 出版时间：December 26, 2013
• 年：2013
• 卷：135
• 期：51
• 页码：19139-19142
• 全文大小：235K
• ISSN：1520-5126

文摘

In contrast to stable phosphorus oxides such as P₄O₆ and P₄O₁₀ that possess iconic adamantane-like cage structures, highly reactive phosphorus oxides such as PO, PO₂, and P₂O_x (x = 1鈥?) only have been studied in the gas phase or by matrix isolation techniques. Elusive diphosphorus tetroxide, the long sought phosphorus analogue of N₂O₄, is particularly noteworthy. Computations predict that the oxo-bridged O₂POPO form of P₂O₄ is energetically more favored than the P鈥揚 bonded O₂P鈥揚O₂ isomer. Herein, we report the experimental realization of diphosphorus tetroxide鈥攊n its energetically disfavored O₂P鈥揚O₂ form鈥攙ia carbene-stabilization. The synthesis of the title compound involves the splitting of molecular oxygen by carbene-stabilized diphosphorus.