Alkane radical cations

Recently, detailed kinetic studies of the hybrid[type II , 02 - type RH] photo-oxidations of cyclohexane and cyclohexane-dn in both NaY and BaY have been reported. A kinetic isotope effect kulko of 5.7 was determined for X > 400 nm in BaY. This substantial isotope effect, which is nearly identical to the isotope effect on the kinetic acidity of cyclohexane, requires that the proton abstraction step, k, in the alkane radical cation superoxide ion pair be smaller than the back-electron transfer, k, to regenerate the charge-transfer complex (Fig. 18). If kpT were larger than k, the rate expression, Eq. (A) in Fig. 18, would be reduced to Eq. (B) and only a small isotope effect on et would be anticipated. 

The Jovian moon, lo, shows an orange hue (Fig. 6.1), which may be due to long-chain alkane radical cations. The atmosphere of lo consists mostly of methane deep UV photolysis proceeds with electron ejection thus, the molecular ion of methane was perhaps the earliest organic radical cation, generated by solar irradiation aeons ago. 

He ( impact (PES) in the gas phase, but oxidation in solution is difficult. Alkane radical cations have become readily accessible only with the advent of matrix isolation techniques combined with ESR detection. 

Scheme 1. The structures of representative alkane radical cations.

For non-electrophilic strong oxidants, the reaction with an alkane typically follows an outer-sphere ET mechanism. Photoexcited aromatic compounds are among the most powerful outer-sphere oxidants (e.g., the oxidation potential of the excited singlet state of 1,2,4,5-tetracyanobenzene (TCB) is 3.44 V relative to the SCE) [14, 15]. Photoexcited TCB (TCB ) can generate radical cations even from straight-chain alkanes through an SET oxidation. The reaction involves formation of ion-radical pairs between the alkane radical cation and the reduced oxidant (Eq. 5). Proton loss from the radical cation to the solvent (Eq. 6) is followed by aromatic substitution (Eq. 7) to form alkylaromatic compounds. 

The pulse radiolysis studies of liquid alkanes have relevance to the radiolysis of polyethylene and related polymers. In liquid alkanes at ambient temperature, the reaction intermediates such as alkane radical-cations, olefin radical-cations, olefine dimer-cations, excited states, and alkyl radicals have been observed after the electron-pulse irradiation [90-93]. According to the nanosecond and subnanosecond studies by Tagawa et al., the observed species were alkane radical cations, excited states, and alkyl radicals in n-dodecane excited states and cyclohexyl radical were observed in cyclohexane, and only radicals in neopentane [91, 93]. Olefin radical-cations were also detected in cyclohexane containing carbon tetrachloride [92],... 

The alkane radical-cations generated in electron-pulse irradiated n-dodecane show an absorption band in the visible with its maximum at 800 nm (Fig. 15) [93], The position of the absorption maximum changed from 600 nm to 900 nm depending on the carbon number of the alkane. It was noted that the lifetime of alkane-radical cations was shorter than that of the solvated electrons observed in the near infrared region. These phenomena were interpreted in terms of the following ion-molecular reaction. 

Recent synchrotron radiation experiments showed that the probability of the energy deposition on the alkane molecules was the highest at about 16 18 eV [95]. With the energies above 16 eV, excited states of alkane radical cations can be produced efficiently. In irradiated cyclohexane, for example, the following reactions were considered to be the formation reactions of alkyl radical. 

Ethylene-propylene copolymer films gave a very broad absorption in the visible region upon electron-pulse irradiation (Fig. 16) [93], It was comprised of at least three species, electrons, excited states, and alkane radical cations. At about 700 nm and 800 nm the contributions from excited states and radical cations, respectively, were largest. The lifetime of the radical cation determined... 

In a combined experimental and theoretical study, Borovkov et alP examined the properties of w-alkane radical cations in solution. Here, we shall just focus on one single aspect of their work, i.e., the conformers of one of the alkanes, w-nonane, C9H2o-In its simplest form of the highest symmetry, its structure can be described as a zigzag chain formed by the 9 carbon atoms. To each of the carbon atoms, 2 hydrogen atoms... 

C-H and C-C bond cleavage in a radical cations is feasible, but not a versatile option for synthetic use because of the very high oxidation potentials. Deprotonations in alkane radical cations have strongly negative Gibbs energies, with strong preference for tertiary over secondary or primary C-H bonds [118]. C-C bonds are selectively weakened in strained carbocycles [119]. 

Among the various conversions discussed in this section, deprotonation is clearly a general reaction of alkane radical cations. The interesting elimination or fragmentation reactions, on the other hand, seem to be zeolite-specific reactions without precedent in halogen containing matrices. 

Proton Transfer from Alkane Radical Cations to Alkanes... 

Three major types of cationic species that can be derived from saturated hydrocarbons are alkyl carbenium ions (R+), alkane radical cations (RH +) and alkyl carbo-nium ions (RH2+). The term carbocations is usually reserved to denote alkyl carbenium and carbonium ions only. Pentacoordinated alkyl carbonium ions (proton-ated alkanes) are the species that result from protonation of alkane molecules they are of paramount importance as reactive intermediates/transition states in the initiation of (Br0nsted) acid-catalyzed conversions of saturated hydrocarbons. Upon dissociation of alkyl carbonium ions, trivalent alkyl carbenium ions are formed and these are responsible for the further progression of acid-catalyzed conversions of alkanes. Alkyl carbenium ions may also be formed by ionization of neutral alkyl radicals and by proton addition to olefins. In both carbenium and carbonium ions, the positive charge is very much located on a particular part of the cation. 

Radical cations of saturated hydrocarbons have strong electronic absorptions in the visible and near-infrared region of the spectrum. The strongly colored nature of alkane radical cations is in striking contrast to neutral alkanes that absorb electronically only in the vacuum UV. The electronic absorption of alkane radical cations has been studied in the solid phase by matrix isolation using y-irradiation [1-3] and in the gas phase by ion cyclotron resonance (ICR) photodissociation in either the steady-state or pulsed mode of operation [4]. Both methods have their specific merits and drawbacks. A major concern in matrix isolation spectroscopy is spectral purity (because of the possible presence of other absorbing species) and... 

The strong electronic absorption of alkane radical cations is readily understood in molecular orbital terms. Extending down from the highest occupied molecular orbital (HOMO) is a rather closely packed set of valence molecular orbitals, that are clearly displayed in the photoelectron spectra (PES) of neutral alkanes. The electronic absorption of alkane radical cations is due to transitions (induced by photon absorption) of electrons from such lower-lying molecular orbitals to the semi-occupied molecular orbital (SOMO), which is the highest-occupied molecular orbital in the ground-state ion. By illumination within the (broad and largely unstructured) absorption band of alkane radical cations, electronically excited states of alkane radical cations can thus be created in a quite convenient way. 

The paramagnetic absorption of alkane radical cations is critically dependent on their conformation. In neat n-alkane crystals, alkane molecules are in the extended all-trans conformation (see Fig. 5.1) and FDMR spectroscopy unequivocally shows that alkane radical cations retain that conformation in such systems. The extended all-trans conformation is also the preferred conformation of many n-alkane radical cations in chlorofluorocarbon and perfluorocarbon matrices. In this conformation, the unpaired electron occupies the planar cr molecular orbital and delocalizes over the entire extended chain. Only two C-H bonds (both chain-end, one on each side) are in the planar ct molecular frame in the extended structure and high unpaired-electron and positive-hole density appears only on these in-plane protons. Alkane radical cations in the extended conformation (as well as in other conformations) are thus fj-delocalized paramagnetic species. The associated hyperfme interaction with the two (equivalent) in-plane chain-end protons results in a 1 2 1 three-line (triplet) EPR spectrum. The fact that the hyperfme in-... 

---