Betaine–Carbene Interconversions. From N-Ylides to Zwitterionic N-Heterocyclic Carbene–Borane Adducts

Abstract

In the presence of NBS 3-methylindole reacted with various imidazoles to give the (indol-2-yl)imidazolium salts 21a-f, which were converted in aqueous solution into the 2-(imidazolium-3-yl)-3-methylindolates 22a-f by base. These conjugated ylides--which represent a subclass of mesomeric betaines--are the exclusively detectable form in the NMR spectra taken in DMSO-d(6). A DFT calculation revealed that the betaine 22a is -9.3 kJ/mol more stable than the tautomeric N-heterocyclic carbene 23a and that the energy for the betaine-carbene interconversion is ΔG(‡) = 66.4 kJ/mol. The N-heterocyclic carbenes (3-methyl-indol-2-yl)imidazol-2-ylidenes, however, can be trapped by sulfur, triethylborane, and triphenylborane. Whereas the first trapping reaction yielded the expected imidazolethiones, the borates gave the first representatives of new zwitterionic borane adducts, imidazo[2',1':3,4][1,4,2]diazaborolo[1,5-a]indolium-11-ides 26a-h. We performed DFT calculations on the structures of mesomeric betaine 22a, the carbene 23a, and the mechanisms of the borane adduct formation to 26a-h, NMR spectroscopic investigations including (15)N, (7)Li, and (11)B NMR spectroscopy, and an X-ray single-crystal analysis of one of the borane adducts.