Journal
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
Volume 136, Issue 17, Pages 6251-6254Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ja502675d
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Funding
- National Natural Science Foundation of China [91122019, 21171087]
- Major State Basic Research Development Program [2013CB922101]
- Natural Science Foundation of Jiangsu Province [BK2011549]
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Two phosphorus-containing four-membered ring radical cations 1(center dot+) and 2(center dot+) 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(center dot+) has elongated P-P bonds and more pyramidalized phosphorus atoms, while shortened P-Min distances and larger angles around phosphorus centers are observed for 2(center dot+) EPR studies indicate that for 1(center dot+) spin density mainly resides on the exocyclic nitrogen atoms with very minor contribution from endocyclic phosphorus atoms, while the situation is opposite for 2(center dot+) Such an inverse spin density distribution is controlled by the exocyclic substituents, which is supported by DFT calculations.
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