Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 54, Issue 9, Pages 2776-2779Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201410276
Keywords
activation; biradicaloids; carbon monoxide; phosphorus; radicals
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Funding
- GDCh
- DFG [SCHU 1170/11-1]
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Diphosphadiazanediyl, [(-NR)P](2) (R=Ter=2,6-dimesitylphenyl), is known to readily activate small molecules with multiple bonds. CO is an especially intriguing species for activation, because either 1,1- or 1,2-bridging mode would lead to a [1.1.1]bicycle or a carbene, respectively. The activation of CO with diphosphadiazanediyl already occurs at ambient temperatures (1bar, 25 degrees C). However, CO is involved in an unprecedented ring expansion reaction under preservation of the biradical character, which leads to the formation of the first stable cyclopentane-1,3-diyl analogue displaying photochromic molecular switch characteristics.
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