Two Stable Phosphorus-Containing Four-Membered Ring Radical Cations with Inverse Spin Density Distributions

Two phosphorus-containing four-membered ring radical cations 1 •+ and 2 •+ have been isolated and characterized by UV–vis absorption spectroscopy, electron paramagnetic resonance (EPR), and single-crystal X-ray diffraction. Compared with neutral molecules 1 and 2, radical 1 •+ has elongated P–P bond...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2014-04, Vol.136 (17), p.6251-6254
Main Authors: Su, Yuanting, Zheng, Xin, Wang, Xingyong, Zhang, Xuan, Sui, Yunxia, Wang, Xinping
Format: Article
Language:English
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Summary:Two phosphorus-containing four-membered ring radical cations 1 •+ and 2 •+ have been isolated and characterized by UV–vis absorption spectroscopy, electron paramagnetic resonance (EPR), and single-crystal X-ray diffraction. Compared with neutral molecules 1 and 2, radical 1 •+ has elongated P–P bonds and more pyramidalized phosphorus atoms, while shortened P–Nring distances and larger angles around phosphorus centers are observed for 2 •+. EPR studies indicate that for 1 •+ spin density mainly resides on the exocyclic nitrogen atoms with very minor contribution from endocyclic phosphorus atoms, while the situation is opposite for 2 •+. Such an inverse spin density distribution is controlled by the exocyclic substituents, which is supported by DFT calculations.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja502675d