The mechanisms of formation of a [2]catenane and one of its molecular components have been investigated. While the synthesis of the tetracationic cyclophane, [BBIPYBIXYCY]4+ from bipyridine (BP) and 1,4-bis(bromomethyl)benzene (BBB), directed by the template, 1,5-bis[2(2-hydroxyethoxy)ethoxy]naphthalene(1/5 BHEEN) becomes less efficient (23 to 5%) under ultra-high pressure reaction conditions (12 kbars), the self-assembly of {[2]-[BPP34C10]-[BBIPYBIXYCY] catenane)4+ from BP and BBB in the presence of BPP34C10 can be achieved with increased efficiency (I 8 to 42%) at 12 kbars. This difference in the trends of the yields can be ascribed to the enhanced templating action of BPP34C10 relative to that of 1/5 BHEEN when two moles of BP and two moles of BBB are being employed to construct the tetracationic cyclophane. The self-assembly of the [2]catenane from BP, BBB, and BPP34C10 has been followed by H-1 NMR spectroscopy in d7-DMF solution. On the basis of this spectroscopic evidence and supporting chemical data, the formation of {[2]-[BPP34C10]-[BBIPYBIXYCY] catenane}4+ from two moles of BP, two moles of BBB, and one mole of BPP34C10 is believed to proceed via the monoquaternary intermediate, [MBXYBIPY]+, which has not been isolated, and the dicationic species, [BBIPYXY]2+, which has been isolated and shown to be an intermediate in the self-assembly process leading to the [2]catenane, presumably via the [BXYBBIPYXY]3+ trication - the final intermediate which again has not been isolated.
