Cage dications

Reduction of the diester 91 yielded the bis(hydroxymethyl)octahedrane 97. Treatment of 97 with superacid led to the interesting cage dication 98 which according to its NMR data must be regarded as a bis(bicyclobutonium) ion (Scheme 21) [78]. The positive charge in the dication 98 is significantly delocalized into the cyclopropane rings. 

Patriksson, A. Adams, C. Kjeldsen, F Raber, J. van der Spoel, D. Zubarev, R. A. Prediction of N-C-alpha bond cleavage frequencies in electron capture dissociation of Trp-cage dications by force-field molecular dynamics simulations. Int. J. Mass Spectrom. 2006, 248, 124-135. 

Diamines with a cage-like structure in which the nitrogen atoms are separated by a three carbon chain, form radical-cations where the non-bonding orbital from one nitrogen atom interacts with the radical-cation on the other nitrogen atom to form a three-electron bond [76]. Cyclic voltammetry of 16 in acetonitrile shows two reversible waves with E° = 0.11 and 0.72 V vs. see. The second wave is due to the formation of a dication with a tw o-electron bond between the nitrogen atoms. 

A different novel cage is prepared by treating Cl2 TeTeNSN with a threefold excess of AsF5 in S02 at 22°C (12 h), giving a 58% yield of a dithiadi-telluratetrazocinium dication (see Scheme 22). The structure as elucidated by X-ray crystallography is an 8-membered ring with a Te-Te (2.881 A)... 

The covalent capsules 227-230 are reported in [162] to form host-guest complexes with encapsulated aromatic dications 92 and 93 by Scheme 2.149. In solution and gas phase, only 1 1 cage complexes have been detected by H NMR and ESI-MS methods. In the case of 228 its 2 1 cage complex with paraquat dicationic guest 92 has been characterized by X-ray diffraction... 

A comparative study of the binding properties of 32-crown-lO-based capsules 227 and 244 toward diquat dication has been performed in [170], These ligands gave 1 1 cage complexes by Scheme 2.150 those have been characterized using H NMR spectra and by X-ray diffraction experiments. As follows from X-ray diffraction... 

The cw-dibenzo-24-crown-8- and his(meta-phenylene)-32-crown-10-based capsules 227 and 252 (see Sect. 2.3.1) are described in [177] to form host-guest 1 1 and 2 1 cage complexes (Scheme 2.156), respectively, with an encapsulated A -methylated l,2-bis-(4-pyridinium)ethane dication. In them, the Af-methyl group of this... 

Threefold- and tetrafold-symmelric ligand syntones 123-128 have been used in [21] for the design of Dja- and D a-symmelric hydrogen-bonded capsules and their analogs. Dimerization and hybridization of these syntones by Schemes 3.20 and 3.21 gave homo- and heterodi-meric ligands 323-329, respectively, which form 1 1 cage complexes with varions encapsulated mono- and dications shown in these Schemes. 

---