Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 20, Issue 6, Pages 1630-1637Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201303705
Keywords
boron; boryl radicals; Lewis bases; spin density; substituent effects; synergistic effects
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Funding
- Xi'an Jiaotong University
- China Postdoctoral Science Foundation [2013M542354]
- National Science Foundation of China [21202129]
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Boryl radicals have the potential for the development of new molecular entities and for application in new radical reactions. However, the effects of the substituents and coordinating Lewis bases on the reactivity of boryl radicals are not fully understood. By using first-principles methods, we investigated the spin-density distribution and reactivity of a series of boryl radicals with various substituents and Lewis bases. The substituents, along with the Lewis bases, only affect the radical reactivity when an unpaired electron is in the boron p(z) orbital, that is, for three-coordinate radicals. We found evidence of synergistic effects between the substituents and the Lewis bases that can substantially broaden the tunability of the reactivity of the boryl radicals. Among Lewis bases, pyridine and imidazol-2-ylidene show a similar capacity for stabilization by delocalizing the spin density. Electron-donating substituents, such as nitrogen, more efficiently stabilize boryl radicals than oxygen and carbon atoms. The reactivity of a boryl radical is always boron based, irrespective of the spin density on boron.
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