Journal
CHEMICAL SCIENCE
Volume 1, Issue 2, Pages 234-241Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c0sc00143k
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Funding
- Israel Science Foundation
- USA-Israel Binational Science Foundation
- Minerva Foundation in Munich
- Center for Absorption in Science, Israel, Ministry of Immigrant Absorption, State of Israel
- National Science Foundation
- Ministry of Education, Science and Technology [R33-10082]
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Stable N-heterocyclic carbenes and germylenes were allowed to react with a phosphonyl radical, (i-PrO)(2)(O)(P) over dot (7), generated by photolysis of [(i-PrO)(2)(O)P](2)Hg. The products were identified by EPR spectroscopy. An unsaturated carbene (1) and germylene (3) react with 7 at the divalent atom to give unstable radical products (tau(1/2) = 0.2 s). A benzo-annulated carbene (4) and a saturated germylene (6) react with 7 to give more active radicals. An unsaturated (2) and a saturated silylene (5) undergo rapid reaction (in the dark) with [(i-PrO)(2)(O)P](2)Hg to yield unusual silyl phosphites. In these cases only secondary radicals were observed. DFT (PBE0/TZVP//B3LYP/6-3]+ G(d)) calculations of the radical adducts of the different (C, Si, Ge) unsaturated N-heterocyclic divalent species with the phosphonyl radical show that the unpaired electron is delocalized over the five-membered ring; the spin density on the central atoms decreases in the order C, 39% > Si, 14% > Ge, 2%. These trends can be understood in terms of a zwitterionic structure of the radical adducts. The calculations of the radical adducts of 4, 5 and 6 with 7 indicate larger spin density on the central atom, 47%, 58% and 42% on C, Si, Ge, respectively.
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