Cation-it interactions

Arnal-Herault, C., Barboiu, M., Petit, E., Michau, M. and van der Lee, A. (2005) Cation-it interaction A case for macrocycle-cation it-Interaction by its ureidoarene counteranion. 

With the knowledge that 14 can activate aldehydes in 1, the role of 1 in the reaction was explored further. Specifically, the relative rates of C—H bond activation and guest ejection, and the possibility of ion association with 1, were investigated. The hydrophobic nature of 14 could allow for ion association on the exterior of 1, which would be both cn t h al pi cal I y favorable due to the cation-it interaction, and entropically favorable due to the partial desolvation of 14. To explore these questions, 14 was irreversibly trapped in solution by a large phosphine, which coordinates to the iridium complex and thereby inhibits encapsulation. Two different trapping phosphines were used. The first, triphenylphosphine tris-sulfonate sodium salt (TPPTS), is a trianionic water-soluble phosphine and should not be able to approach the highly anionic 1, thereby only trapping the iridium complex that has diffused away from 1. The second phosphine, l,3,5-triaza-7-phosphaadamantane (PTA), is a water-soluble neutral phosphine that should be able to intercept an ion-associated iridium complex. 

Gallivan, J.P. and Dougherty, D.A. (1999) Cation—It interactions in structural biology. Proceedings of the National Academy of Sciences of the United States of America, 96, 9459—9464. 

Fig. 18.6 (a) Demonstration of cooperativity between cation-it interaction and hydrogen bonding... 

Synthetic receptors such as cyclophanes can substantially exploit the cation-ir interaction in binding (see Section 4.2.5). Also, in crystal packing and many catalytic systems, cation-iT interactions can be important players. 

The effect of the bond dipole associated with electron-withdrawing groups can also be expressed in terms of its interaction with the cationic u-complex. The atoms with the highest coefficients in the LUMO 3 are the most positive. The unfavorable interaction of the bond dipole will therefore be greatest at these positions. This effect operates with substituents such as carbonyl, cyano, and nitro groups. With ether and amino substituents, the unfavorable dipole interaction is overwhelmed by the stabilizing effect of the lone-pair electrons stabilizing 3. 

Experimental reactivity patterns are based on solution behavior which are influenced by interactions between solvent and reacting molecules (especially ions). Compare electrostatic potential maps of 2-methyl-2-propyl cation and dimethylhydroxy cation. Identify sites that might form strong hydrogen bonds with water. Which ion will be better stabilized by its interaction with water ... 

E. Hydrated divalent cation approaching a channel with a slightly larger diameter than in D, but the energy of interaction with the divalent cation is sufficient to deform the channel drawing the walls in to make lateral coordination with the divalent cation. Since the channel is too small for a monovalent cation to pass through with its first hydration shell and since the monovalent cation channel interaction is insufficient to make the channel small enough for lateral coordination of the monovalent cation, the channel is selective for divalent cations. (Part E reproduced with permission from Ref. 68 )... 

The composition of the electrolyte is quite important in controlling the electrolytic deposition of the pertinent metal, the chemical interaction of the deposit with the electrolyte, and the electrical conductivity of the electrolyte. In the case of molten salts, the solvent cations and the solvent anions influence the electrodeposition process through the formation of complexes. The stability of these complexes determines the extent of the reversibility of the overall electroreduction process and, hence, the type of the deposit formed. By selecting a suitable mixture of solvent cations to produce a chemically stable solution with strong solute cation-anion interactions, it is possible to optimize the stability of the complexes so as to obtain the best deposition kinetics. In the case of refractory and reactive metals, the presence of a reasonably stable complex is necessary in order to yield a coherent deposition rather than a dendritic type of deposition. 

It appears that Te is more flexible in the possible arrangements (Figure 18) 72,73 it should be noted though that the counterions of these Te cations are more basic than the fluorinated anions used for S and Se cations. Thus, it may well be that the structural flexibility of the Te cations is a result of the increased cation-anion interactions in these salts. 

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