Deutliche Belege für Ein-Elektronen-Übertragungen in der Boryl-Anionenchemie: Isolierung und Reaktivität eines neutralen Borolradikals

Nucleophilic, anionic boryl compounds are long-sought but elusive species. We report that reductive cleavage of the boron-bromine bond in N,N'-bis(2,6-diisopropylphenyl)-2-bromo-2,3-dihydro-1H-1,3,2-diazaborole by lithium naphthalenide afforded the corresponding boryllithium, which is isoelectronic with an N-heterocyclic carbene. The structure of the boryllithium determined by x-ray crystallography was consistent with sp(2) boron hybridization and revealed a boron-lithium bond length of 2.291 +/- 0.006 angstroms. The structural similarity between this compound and the calculated free boryl anion suggests that the boron atom has an anionic charge. The (11)B nuclear magnetic resonance spectrum also supports the boryl anion character. Moreover, the compound behaves as an efficient base and nucleophile in its reactions with electrophiles such as water, methyl trifluoromethanesulfonate, 1-chlorobutane, and benzaldehyde. Show more

Shortly after their discovery at the end of the 80s, stable singlet carbenes have been recognized as excellent ligands for transition metal based catalysts, and as organo-catalysts in their own right. At the end of the 2000s, it has been shown that they can coordinate main group elements in their zero oxidation state, and even activate small molecules. This review covers examples in the literature dealing with the most recent application of stable singlet carbenes, namely their use to stabilize radicals and radical ions that are otherwise unstable. Show more