Reactivity of a Super‐Electron‐Rich Olefin Derived from Cyclam

Abstract A series of new compounds has been synthesised from an electron‐rich olefin derived from cyclam ( A ). Thus, A reacts with oxygen gas to give the syn ‐bis(urea) 1 and with sulfur to yield the anti ‐bis(thiourea) 2 . The reaction of A with triflic acid furnishes the bis(imidazolium) triflate 3 , which gives the monoprotonated imidazolium salt 4 upon treatment with sodium tetraphenylborate in water. Theoretical calculations (DFT) predict the diprotonated species to be energetically disfavoured, thus demonstrating the importance of hydrogen‐bonding interactions. Treatment of compound 3 with silver oxide affords the di‐ and monoprotonated cationic salts 5a and 5b in THF and dichloromethane, respectively. The molecular structures of compounds 1 , 2 , 3 , 4 , 5a and 5b have been established by X‐ray diffraction. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)