Dimers solvent effects

This interesting solvent effect was explained by Baro et al. on the basis of the formation of cyclic dimers (13.7) as suggested earlier by Hunter (1937) and by Le Fevre and Vine (1937). It was later confirmed in an X-ray investigation by Omel chenko and Kondrashev (1967). The X-ray analysis of 1,3-diphenyltriazene copper(i) (Brown... 

The diradical mechanism b is most prominent in the reactions involving fluorinated alkenes. These reactions are generally not stereospecificand are insensitive to solvent effects. Further evidence that a diion is not involved is that head-to-head eoupling is found when an unsymmetrical molecule is dimerized. Thus dimerization of F2C=CFC1 gives 106, not 107. If one pair of electrons moved before the other, the positive end of one molecule would be expeeted to attack the negative end of the other. 

Azo-bridged ferrocene oligomers also show a marked dependence on the redox potentials and IT-band characteristics of the solvent, as is usual for class II mixed valence complexes 21,22). As for the conjugated ferrocene dimers, 2 and 241 the effects of solvents on the electron-exchange rates were analyzed on the basis of the Marcus-Hush theory, in which the t/max of the IT band depends on (l/Dop — 1 /Ds), where Dop and Ds are the solvent s optical and static dielectric constants, respectively (155-157). However, a detailed analysis of the solvent effect on z/max of the IT band of the azo-bridged ferrocene oligomers, 252,64+, and 642+, indicates that the i/max shift is dependent not only on the parameters in the Marcus-Hush theory but also on the nature of the solvent as donor or acceptor (92). 

Dimers (73) and (74) were formed in approximately equal amounts in all cases, although, as in the cases of 2-cyclopentenone and 2-cyclohexenone, the relative amount of (72) (either cis-syn-cis or cis-anti-cis) was found to vary substantially with solvent polarity. As in 2-cyclopentenone, this increase in the rate of head-to-head dimerization was attributed to stabilization of the increase in dipole moment in going to the transition state leading to (72) in polar solvents. It is thought that the solvent effect in this case is not associated with the state of aggregation since a plot of Stem-Volmer plot and complete quenching with 0.2 M piperylene indicate that the reaction proceeds mainly from the triplet manifold. However, the rates of formation of head-to-head and head-to-tail dimers do not show the same relationship when sensitized by benzophenone as in the direct photolysis. This effect, when combined with different intercepts for head-to-head and head-to-tail dimerizations quenched by piperylene in the Stem-Volmer plot, indicates that two distinct excited triplet states are involved with differing efficiencies of population. The nature of these two triplets has not been disclosed. 

The metastable species involved in these reactions may be either excited charge-transfer complexes or biradicals, although a charge-transfer complex would be expected to result in a predominance of head-to-head dimers. Dipole effects, on the other hand, would favor formation of head-to-tail dimers, especially in relatively nonpolar solvents ... 

Incidently, the observed solvent effect may be supportive evidence against incursion in nonpolar solvents of a second reactive 3n-n state.129. 130) The zn-n state would be expected to be less selective for the head-to head dimer since one of the principle stabilizing interactions is missing. 

The future prospects for the capsule project emerge from these considerations. Further increasing the size of the capsule and building chemical functionalities into the inner cavity would allow a closer emulation the functions of enzymes, especially those that require cofactors in order to catalyze chemical transformations. Another important aspect is to design capsules that can combine stereospecificity and catalysis - that is accelerate stereoselective transformations. Capsules that reversibly dimerize in water would probably contribute a lot more to our understanding of non-covalent forces and solvent effects in this most biorelevant medium. So far, water solubility and assembly have not been achieved with hydrogen-bonded capsules. 

At first glance the Diels-Alder reaction represents an organic transformation which is relatively insensitive to solvent effects (Table 9). For the dimerization of cyclopentadiene, the second-order rate constants in a broad range of organic solvents are quite similar5. The data of Table 9 refer to the special case of a Diels-Alder reaction between two pure hydrocarbons. Usually, Diels-Alder reactions only proceed at an appreciable rate when either the diene or the dienophile is activated by electron-donating or electron-withdrawing... 

Careful quantitative kinetic studies of the coupling steps of oKgomeric pyrroles and thiophenes have confirmed this mechanistic pattern [49]. In addition, quantum chemical studies reveal that the dimerization of two radical cations becomes perfectly feasible when solvent effects are included [50]. 

Meso-dl isomerization of [47] was described by Koch (Koch et ah, 1975 Koch, 1986 Olson and Koch, 1986. The intermediate radical [48] is in equilibrium with the dimer and can be easily recognized by esr spectroscopy. The thermodynamic parameters for bond homolysis, as a function of medium, are reported in Table 18. A strong solvent effect is observed, in contrast to Riichardt s example ([24], [25]) reported above. This is interpreted as a manifestation of the polar character of the intermediate radical. The easy detection of [48] by esr spectroscopy is traced back, at least in part, to its captodative character. However, the strong solvent effect on homolysis of [47] need not necessarily be related to the captodative character of radicals [48]. 

Solvent Effects. As noted earlier, Netzel et al. (M- ) observed striking effects on the photodynamics of electronically excited MgP-P dimers depending on the solvent used. For example, in their earlier work (20) they showed that the photodynamics in CH2CI2 were consistent with the formation of a long-lived singlet CT state which decayed by two pathways, while in THF only a single short-lived (tt, tt ) state was observed. 

Closely related to solvent effect, and governed by the same or similar factors, are the phenomena of dimerization via self-association, and association with other species present in solution, such as cations or anions, in definite stoichiometric proportions. Studies of such associations lead to further knowledge of such interactions involving the more complex bases in nucleic acid structures. One of the earliest workers to study dimerization systematically was Shindo (59CPB407), who examined the broad N—H stretch region 3300-2400 cm-1 in the IR spectra of a variety of substituted pyridin-2-ones and quinolin-2-ones in perfluorocarbon mulls and CC14 solution. 

The characteristic features of hydroboration of alkenes—namely, regioselec-tivity, stereoselectivity, syn addition, and lack of rearrangement—led to the postulation of a concerted [2 + 2] cycloaddition of borane353,354 via four-center transition state 37. Kinetic studies, solvent effects, and molecular-orbital calculations are consistent with this model. As four-center transition states are unfavorable, however, the initial interaction of borane [or mentioned monobridged dimer, Eq. (6.56)] with the alkene probably involves an initial two-electron, three-center interaction355,356(38, 39). 

Cyclic enones participate in several other photochemical reactions. Irradiation of neat cyclopentenone417 or cyclohexenone418 leads to formation of dimers. Eaton has shown that the reaction is quenched by piperylene and that there is a strong polar solvent effect on the ratio of head-to-head and head-to-tail dimers formed.511 Similar solvent effects have been noted for the triplet-state photodimerization of isophorone.512 Head-to-head dimers are favored in polar solvents and in neat ketone, while head-to-tail dimers are favored in nonpolar media. 

Another example of a carbonyl compound whose excited singlet reacts before crossing over to a triplet is provided by coumarin. Direct irradiation in ethanol gives very low yields of a cw-fused dimer.432 However, inclusion of benzophenone results in only trans-fused dimer, even if all the light is initially absorbed by the coumarin.433 Apparently, excited singlet coumarin transfers its singlet excitation to benzophenone, which then crosses over to its triplet and transfers its triplet excitation to coumarin. Triplet coumarin then dimerizes fairly efficiently ( = 0.25) to a tranj-fused system. Morrison has demonstrated sizeable solvent effects on this photodimerization.434 Yields of the cis-dimer are increased by polar solvents and probably arise from excited singlet excimers.119... 

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