Charge transfer complexes constants

TABLE 4.5 Charge Transfer Complex Constants C and C2 for equation 4.27 (in eV)... 

Table 1. Charge Transfer complex constants for poly(N-(9-carbazole 4-butyryl) ethyleneimine) and 9-carbazole butyronitrile.

Equilibrium constants for complex formation (A") have been measured for many donor-acceptor pairs. Donor-acceptor interaction can lead to formation of highly colored charge-transfer complexes and the appearance of new absorption bands in the UV-visible spectrum may be observed. More often spectroscopic evidence for complex formation takes the font) of small chemical shift differences in NMR spectra or shifts in the positions of the UV absorption maxima. In analyzing these systems it is important to take into account that some solvents might also interact with donor or acceptor monomers. 

The ability of compounds with double bonds to act both as electron donors and as electron acceptors in charge transfer complex formation is well known (81,82). Hammond (83) has studied the correlations of association constants and of the energy of the charge transfer absorption of 2-substituted-l,4-benzoquinones complexed with hexamethylbenzene with the Hammett equation. Charton (84) has studied the correlation with eq. (2) of association constants of 1-substituted propenes with Ag. ... 

Sufficient data are extant for three sets of charge transfer complex association constants and one set of charge transfer absorption energies. The sets studied are reported in Table XV. Results of the correlations with eq. (2) are given in Table XVI. All the sets studied gave significant results. An improvement in the correlation for set 15-2 occurs on the exclusion of the values for X = Ac and X = COaMe (set 15-2BA). 

Table 1 Formation constant and spectral characteristics of bromide (charge-transfer) complexes with various acceptorsa...

Charge-transfer complexes between heteroaromatic five-membered ring compounds and tetracyanoethylene have been studied in solution at 20°C.22 Spectra, stability constants, and empirical calculations of ionization energies... 

A relatively strong organization of an electron donor by an acceptor is typically indicated by experimental values of KEUA or KC f> > 10 M-1. For intermediate values of the formation constant, i.e., 1 < KE A < 10 m, the donor/acceptor organization is considered to be weak.17 Finally, at the limit of very weak donor/acceptor organizations with KEDA 1, the lifetime of the EDA complex can be on the order of a molecular collision these are referred to as contact charge-transfer complexes.18... 

Table 2 Formation constants of bromine-alkene charge-transfer complexes.

This means that 4-nitrostilbene is a more effective electron acceptor than nitrobenzene. This theoretical conclusion is verified by experiments. The charge-transfer complexes formed by nitrobenzene or 4-nitrostilbene with Af,Af-dimethylaniline have stability constants of 0.085 L mol or 0.296 L mol respectively. Moreover, the formation of the charge-transfer complex between cis-4-nitrostilbene and A/,Af-dimethylaniline indeed results in cis-to-trans conversion (Dyusengaliev et al. 1995). This conversion proceeds slowly in the charge-transfer complex, but runs rapidly after one-electron transfer leading to the nitrostilbene anion-radical (Todres 1992). The cis trans conversion of ion-radicals will be considered in detail later, (see sections 3.2.5.1, 6.4, and 8.2.1). 

Alkali, alkaline-earth, and rare-earth metal cations also catalyze electron transfer reactions. Thus, in the pair of Co -tetraphenylporphyrin complex with BQ, no redox reaction takes place, or it takes place too slowly to be determined. The metal cations promote this reaction. For example, in the presence of 80(0104)3, the corresponding rate constant of 2.7 X 10 M s was observed. BQ transforms into benzosemiquinone under these conditions (Fukuzumi and Ohkubo 2000). Zinc perchlorate accelerates the reaction between aromatic amines and quinones (Strizhakova et al. 1985). This reaction results in the formation of charge-transfer complexes [ArNHj Q ]. The complexes dissociate in polar solvents, giving ion-radicals ... 

Involvement of AModo species in electrophilic C-iodinations needs to be considered since a number of imidazoles are known to form such compounds in basic medium. Charge-transfer complexes, too, are quite well known. They seem to be of the n -type through the unshared electron pair at N-3. Equilibrium constants for their formation are known to increase regularly in line with electron-donating powers of substituents (or vice versa). Some KCT values at 20°C (L M are imidazole (200), 1-methylimidazole (333), 1,2-dimethylimidazole (1165), 4-phenylimidazole (152), and 4,5-diphenylimidazole (141) (83BSB923). The charge-transfer complexes formed between iodine and imidazole-2-thiones appear to involve the sulfur atoms (88JA2586). 

Students assigned to the charge transfer experiment must first find out what constitutes a charge transfer complex. Then they find examples of charge transfer studies from the literature. They usually quickly see that spectrophotometry is commonly used for such studies and that the temperature will need to be varied. The procedure chosen is to determine the equilibrium constant at more than one temperature and from these data, to calculate the thermodynamic parameters. Students generally have difficulty in selecting a system that has an equilibrium constant that is not too big or too small and to select a solvent. This means they need to do some calculations to determine if a reasonable quantity of product is... 

Excitation energy of the first absorption band of charge-transfer complexes (for a constant acceptor) HOMO... 

Correlations between pK,d values and the equilibrium constants for the formation of iodine complexes with imidazoles suggest that the charge transfer complexes are of the /j-type involving donation of the unshared electron pair at N-3. For examples of K and pK3 values are imidazole, 202, 6.95 1-methylimidazole, 333, 7.33 4-phenylimidazole, 152, 6.10 4,5-diphenylimidazole, 141, 5.90 (83BSB923). 

Both t-1 and c-1 form ground state charge-transfer complexes with strong electron acceptors (72-79). Equilibrium constants and absorption data for their complexes with several electron-poor alkenes are given in Table A. The absorption maxima of a family of charge-transfer complexes can be related to the donor ionization potential (IPp) and acceptor electron affinity (EA ) using eq. 16 (79). 

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