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Reactivity of a Super‐Electron‐Rich Olefin Derived from Cyclam
Author(s) -
Lappert Michael F.,
Álvarez Santiago,
Aullón Gabriel,
Fandos Rosa,
Otero Antonio,
Rodríguez Ana,
Rojas Sergio,
Terreros Pilar
Publication year - 2009
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.200801113
Subject(s) - chemistry , olefin fiber , cyclam , thiourea , trifluoromethanesulfonate , dichloromethane , triflic acid , reactivity (psychology) , cationic polymerization , inorganic chemistry , medicinal chemistry , organic chemistry , polymer chemistry , catalysis , pathology , medicine , alternative medicine , solvent , metal
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)