Abstract
A series of functionalized calix[4]arenes were prepared that contain mono- and bis-(alkoxy)imidazolium groups that are linked to the lower rim of a t-butylcalix[4]arene framework. These molecules have potential as anion-complexation reagents and as precursors to N-heterocyclic carbene complexes that are attached to a calixarene framework. They were prepared by the preliminary reaction α,ω-dibromoalkanes with the parent t-butylcalix[4]arene to give bis-ω-bromoalkoxy groups that are connected to the calix[4]arene framework in the 25- and 27-positions. The reaction of the bis-substituted calixarenes with TiCl(4) led to the removal of one bromoalkoxy group to give mono-substituted derivatives. Both the mono- and bis-functionalized calixarenes were reacted with N-substituted imidazoles to give a series of mono- or bis-imidazolium salts with the imidazolium group tethered to the calix[4]arene via O-(CH(2))(n)- linkages (n = 2, 4, or 6). Unexpected bis-calix[4]arene products, in which the calixarenes are linked together via bridging organic groups, were obtained in some of these reactions. One bridge consists of two calixarenes linked together via two -C(2)H(4)- groups while the other had a -O-C(4)H(8)-imidazolium-C(4)H(8)-O- linker tethering the two calix[4]arenes together. Both these species were characterized by single crystal X-ray diffraction studies. The structures both had significant disorder but, nevertheless, the data do establish their structures. That the imidazolium-substituted calix[4]arene cations are precursors to N-heterocyclic carbene complexes of nickel was demonstrated by the reaction of a mono-imidazolium-substituted calix[4]arene with nickelocene to give the fully characterized N-heterocyclic carbene nickel complex linked to the calix[4]arene group.