7r-interactions

Ross, I. G., Trans. Faraday Soc. 48, 973, Calculations of the energy levels of acetylene by the method of antisymmetric molecular orbitals, including a—7r-interaction."... 

Cations are by no means the only species where the effects of hyperconjugative delocalization reveal themselves in such a striking manner. Similar effects exist in neutral systems or in anions. For instance, the normal propyl anion should tend to be eclipsed (E) since in this manner the molecule would optimize the 4-electron interactions between the ethyl group t orbital and the p orbital which carries the electron pair. In the bisected conformation, where ttchs and ttchs have both been raised in energy, the four-electron, destabilizing (see Section 1.7, rule 2) p ->7r interaction is stronger than in the eclipsed conformation. At the same time the two-electron, stabilizing p ->ir interaction is weaker than in the eclipsed conformation. Both effects favor the eclipsed conformation. 

As in molecular chemistry, an alternative path to compensate for electron deficiency is the formation of multiple bonds, through 7r-interactions, as in unsaturated and aromatic molecular systems. Our work in Houston focuses on probing the efficacy of the ZintI concept in rationaUzing stoichiometries, crystal structures and chemical bonding of complex electron-poof ZintI phases that exhibit novel i-systems. Their chemical bonding is reflected by their unusual crystal structures related to unsaturated hydrocarbons [53]. 

Dimeric via OH-tt interactions Monomeric, intramolecular OH-ir interaction Monomeric, intramolecular OH 7r interaction Monomeric, intramolecular OH- it interaction Intramolecular OH-N only Dimers, intermolecular OH - N only Dimers, intermolecular OH---N only Chains, intermolecular OH -N only... 

The only simple diphosphide complex in Table IV is /-Bu-Ga(PHMes ")2,82 which has Ga—P bond lengths averaging 2.325 A. This distance is, with one exception, longer than those observed in the monophosphide complexes. This is consistent with a weak but significant gallium-phosphorus 7r-interaction where competition between two phospho-... 

Two other types of 7r-interaction between boron and carbon centers that merit consideration are bond hyperconjugation (12a and 12b) and homoallylic delocalization (13a, 13b, and 13c, n = 1,2,.. . ), respectively. 

Planar coordination compounds with aromatic ligands, especially those having extended 7r-systems, show 7r-7r interactions in the solid state. The ligands shown in Figure 8 form complexes with silver(I) which have a supramolecular structure through 7r-7r interactions.586-596... 

In some of these type of polymeric materials there are two forces that organize the polymer strands into a supramolecular structure, and are usually hydrogen bonds and 7r-7r interactions, this happens with the complex [l,2,4,5-C6H2 CH20CH2C(pz)3 4Ag2(BF4)2] .605... 

Other supramolecular structures such as catenanes and rotaxanes can be formed using zinc as a template ion for example, a benzylic imine catenate formed by Leigh et a/.288 The reversible five-component assembly of a [2]catenane from a chiral metallomacrocycle and a dinaphtho-crown ether has been achieved. Zinc is used as the metal component and drives assembly via the coordination to a bipyridyl unit 7r interactions between the aromatic components are also... 

H NMR spectra for both hydroquinone and bipyridinium protons indicated 7r-7r interactions. 

The weak interactions that may exist between group 2 cations and anionic hydrocabyl ligands are demonstrated in the metal-in-a-box compounds such as [M(THF)6][Me3Si(fluorenyl)]2 (M = Ca 159 or Mg), which are formed by the addition of THF to solutions of the bis(fluorenyl) complexes in non-polar solvents. The box may be completed by the presence of aromatic molecules, as in 159 (Figure 84). The disruption of the metal-carbon bonds is thought to stem from a combination of robust M-THF interaction, the stability of the free [Me3Si(fluorcnyl)] ion, and the formation of numerous C-H- -7r interactions between THF and the anions. These and related examples are reviewed elsewhere. 

Longer Hg-7r interactions are observed in the /> ra-/-butylcalix[4]arene mercury complex 162. The mercury atom forms primary bonds with the two sulfur atoms and engages in weaker secondary interactions with two arene rings of the calixarene whose centroids sit at 3.07-3.11 A from the metal center.201... 

Unusual arene-cadmium 7r-complexes have been recently prepared and structurally characterized. For example, the /w /zz-bcn/i porphyrin complex 194, which can be obtained by reaction of the free base with CdCl2, possesses a cadmium atom that is bound to the Mfez-phcnylcnc unit of the ligand in an apparent /-fashion (Figure 32). The resulting Cd-C distance of 2.71 A is shorter than the sum of the van der Waals radii.252 Despite this relatively short contact, DFT calculations and AIM analysis point to the weakness of the interaction. Comparable weak arene-cadmium 7r-interactions are also observed in the /wra-benziporphyrin cadmium chloride complex 195.253... 

The common feature of compounds [5]-[15] is that the electrophoric units are linked by saturated spacers, thus establishing only weak electronic (through-bond or through-space) interaction of the Tt-systems. In contrast, the binaphthyl [16], the biperylenyl [17] and the bianthryl [18] as well as the structurally related homologues [19], [20] and [21] allow for a direct 7r,7r-interaction of the subunits it will be shown, however, that for both steric and electronic reasons the inter-ring conjugation can be weak and thus lead to electronically independent redox groups in a similar fashion as in [5]-[15]. 

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