Radical cations unimolecular reactions

New synthetic transformations are highly dependent on the dynamics of the contact ion pair, as well as reactivity of the individual radical ions. For example, the electron-transfer paradigm is most efficient with those organic donors yielding highly unstable cation radicals that undergo rapid unimolecular reactions. Thus, the hexamethyl(Dewar)benzene cation radical that is generated either via CT activation of the [D, A] complex with tropylium cation,74... 

Concerning their structure and reactions, organic radical cations have been the focus of much interest. Among bimolecular reactions, the addition to alkenes and their nucleophilic capture by alcohols, which lead to C—C and C—O bond formation, respectively have been investigated in detail. Unimolecular reactions like geometric isomerization and several other rearrangements have also attracted attention. 

Class (3) reactions include proton-transfer reactions of solvent holes in cyclohexane and methylcyclohexane [71,74,75]. The corresponding rate constants are 10-30% of the fastest class (1) reactions. Class (4) reactions include proton-transfer reactions in trans-decalin and cis-trans decalin mixtures [77]. Proton transfer from the decalin hole to aliphatic alcohol results in the formation of a C-centered decalyl radical. The proton affinity of this radical is comparable to that of a single alcohol molecule. However, it is less than the proton affinity of an alcohol dimer. Consequently, a complex of the radical cation and alcohol monomer is relatively stable toward proton transfer when such a complex encounters a second alcohol molecule, the radical cation rapidly deprotonates. Metastable complexes with natural lifetimes between 24 nsec (2-propanol) and 90 nsec (tert-butanol) were observed in liquid cis- and tra 5-decalins at 25°C [77]. The rate of the complexation is one-half of that for class (1) reactions the overall decay rate is limited by slow proton transfer in the 1 1 complex. The rate constant of unimolecular decay is (5-10) x 10 sec for primary alcohols, bimolecular decay via proton transfer to the alcohol dimer prevails. Only for secondary and ternary alcohols is the equilibrium reached sufficiently slowly that it can be observed at 25 °C on a time scale of > 10 nsec. There is a striking similarity between the formation of alcohol complexes with the solvent holes (in decalins) and solvent anions (in sc CO2). 

Dissociative ionization of [l,2,5]thiadiazolo[3,4-f][ l,2,5]thiadiazole 6 was found to be an efficient preparative route to in j// -generated thionitrosyl cyanide and its radical cation, both of which are stable and did not undergo unimolecular rearrangement under the reaction conditions. The [C,N2,S] ions were characterized by mass spectrometry (ml% 72) (see Section 10.05.3.2.2) <1997JST(418)209>. 

With ions or dipolar substrates, radical ions undergo nucleophilic or electrophilic capture. Nucleophilic capture is a general reaction for many alkene and strained-ring radical cations and may completely suppress (unimolecular) rearrangements or dimer formation. The regio- and stereochemistry of these additions are of major interest. The experimental evidence supports several guiding principles. 

At this time, no absolute rate constants have been determined for a reaction of an aminium cation radical. However, for synthetic utility, one needs to consider the relative rate constants for competing reactions. Competition between two unimolecular reactions depends only upon the relative rate constants for the processes. For competition between a unimolecular and a bimolecular reaction whose rate constants are comparable, product distributions can easily be controlled by the concentration of the second species in the ratio of rate laws. The ratio of reaction products from cyclization (unimolecular) versus hydrogen atom trapping before cyclization (bimolecular) can be expressed by the equation %(42 + 65)/%41 = Ar/(A H[Y - H]) (Scheme 20). Competition between two bimolecular reactions is dependent on the relative rate constants for each process and the effective, or mean, concentration of each reagent. The ratio of the products from H-atom transfer trapping of the cyclized radical versus self-trapping by the PTOC precursor can be expressed by the equation %42/%65 = (kH /kT) ([Y - H]/[PTOC]). 

If fcf > feBET- the overall transformation can occur rapidly despite unfavorable driving forces for the electron transfer itself. Only follow-up reactions with high kf can compete with back electron transfer. Different kinds of such unimolecular processes can drive the equilibria toward the final product. A representative example is the mesolytic cleavage of the C-Sn bond in the radical cation resulting from the oxidation of benzylstannane by photoexcited 9,10-dicyanoanthracene (DCA). This is followed by the addition of the benzyl radical and the tributyltin cation to the reduced acceptor DCA [59]. In the arene/nitrosonium system, [ArH, NO+] complexes can exist in solution in equilibrium with a low steady-state concentration of the ion-radical pair. However, the facile deprotonation or fragmentation of the arene cation radical in the case of bifunctional donors such as octamethyl(diphenyl)methane and bicumene can result in an effective (ET) transformation of the arene donor [28, 59]. Another pathway involves collapse of the contact ion pair [D+, A- ] by rapid formation of a bond between the cation radical and anion radical (which effectively competes with the back electron transfer), as illustrated by the examples in Chart 5 [59]. 

---