Neutral biradicals

An alternative approach to stabilizing the metallic state involves p-type doping. For example, partial oxidation of neutral dithiadiazolyl radicals with iodine or bromine will remove some electrons from the half-filled level. Consistently, doping of biradical systems with halogens can lead to remarkable increases in conductivity and several iodine charge transfer salts exhibiting metallic behaviour at room temperature have been reported. However, these doped materials become semiconductors or even insulators at low temperatures. 

Hehre and co-workers have used this approach for the investigation of biradicals and other reactive neutral molecules. For example, by using the bracketing approach, they were able to determine the proton affinities of o- and p-xylylene (o- and p-quinodimethane (lo and Ip) Figure 5.3), from which they were able to determine the enthalpies of formation of the reactive, Kekule molecules. They found the proton affinity of the meta isomer to be too high to be measured directly by bracketing, but were able to assign a lower limit, and subsequently a lower limit to the enthalpy of formation of the m-xylylene diradicals. 

The strain of cycloproparenes is the principal obstacle that must be overcome in their synthesis. Cycloproparenes decompose usually at moderate temperatures, and they undergo ring-opening in the presence of electrophilic or metallic reagents. In contrast, they support even strongly basic conditions quite well. Accordingly, most successful cycloproparene syntheses use some base-induced elimination in the last step. Alternatively, flash vacuum pyrolytic or photochemical extrusion of a neutral fragment, followed by biradical closure or flash vacuum pyrolysis may be used. In these latter approaches the reaction conditions are neutral, and reactive products may be trapped at low temperatures. 

Scheme 3 Chemical stmctures of neutral tc-radical and biradical molecules of organic conductors...

Since ozone is a strong 1,3-dipole,635 or at least has a strong polarizability (even if a singlet biradical structure is also feasible), it is expected to be readily protonated in superacids, in manner analogous to its alkylation by alkylcarbenium ions. Protonated ozone HC>3+, once formed, should have a much higher affinity (i.e., be a more powerful electrophile) for cr-donor single bonds in alkanes than neutral ozone. 

Quinone methides are strikingly different from the 1,2- and 1,4-isomers, because there is no direct orbital interaction between the meta-oxygen and carbon substituents at the benzene ring. Consequently, the neutral valence bond resonance form for the 1,3-quinone methide is a triplet biradical (Scheme 1). These 1,3-quinone methides are chemically more unstable and difficult to generate than their 1,2- and 1,4-isomers, which exist as stable neutral molecules.8... 

Both we and others have established various radical cation structure types, which deviate in important features from the structures of their neutral diamagnetic precursors. The pursuit of these novel structure types has given new direction to radical cation chemistry. We have noted that some of these species resemble plausible transition structures for the thermal rearrangement of the parent molecules, i.e. saddle points on the corresponding potential surfaces. From a different point of view, they can be envisaged as one-electron oxidation products of biradicals or zwitterions. However, this relationship rarely serves as a practical approach to their generation, since the potential bifunctional precursors are often unstable and not readily accessible. These radical cations are usually generated from related hydrocarbons or cyclic azo compounds. 

In summary, we emphasize that homoaromatic stabilization appears to be more important for radical cations than for their neutral diamagnetic precursors. There are several reasons why radical cations may assume cyclic conjugated structures with 4n + 17i-electrons, one electron shy of the magic 4n + 2 7i-electrons which achieve aromaticity, when the parent molecules opt for a less delocalized nonaromatic structure. The principal cause might lie in the strength of the carbon-carbon single bond, which generally disfavors biradical or zwitterionic... 

Information is also given for excited neutral radicals. Several recent reviews have described the reactions of excited radicals, radical ions, biradicals, carbenes, ylides, and other intermediates. Neutral radicals derived from organic systems... 

The development of the two-color and laser jet approaches has also allowed the study of the photochemical behavior of excited states of reaction intermediates, i.e., transient species that are chemically distinct from the original ground or excited state, such as neutral and ion radicals, biradicals, carbenes, and ylides. In fact, the study of excited reaction intermediates has been more comprehensive than the study of upper states. Originally, the short-lived nature of the ground-state transient itself led to the incorrect assumption that the excited transient would be too short-lived to participate in any chemical or photophysical processes other than deactivation to the ground state. However, this is now known not to be the case and some surprising differences between the ground- and excited-state behavior of reaction intermediates have been observed. 

Another interesting and important feature of collisional reduction of cations is that the reducing electron can enter a high molecular orbital corresponding to an excited state of the neutral molecule, radical, or biradical. The types of excited states are depicted in Fig. 3. Electron capture in a Rydberg-type orbital can give... 

Electron transfer catalyzed cycloadditions via radical cations show remarkable selectivity that could be exploited for expanded synthetic methodology. As a complement to the neutral Diels-Alder reaction, ET catalysis hlls the void of the electron-rich diene/electron-rich dienophile cyclizations. In attempt to understand the intricate details of the reaction, experimentalists and theorists have uncovered a range of novel factors to control and manipulate these high-energy reactive intermediates. As exemplihed by the cases discussed in this contribution, the charged character of the intermediates and the presence of back electron transfer leading to the biradical reaction manifold opens new pathways to control the chemo-, peri-, and stereochemical patterns in these dynamic species. 

The reaction affords two products, an oxolane Pi and an oxetane P2, which exhibit a mirror-image relationship of their CIDNP patterns. The three most strongly polarized signals, of Hi, H7, and H7, with intensity ratios of about —2 to + 3 to +3.5, have been shown in the figure all the other protons are also polarized, but more weakly. The observed pattern is found to be in excellent agreement with the relative proton hyperfine coupling constants of the neutral benzosemiquinone radical and of the tert-butoxybicyclo[2.2.1]heptenyl radical, which were tested as model compounds for the two radical moieties.The biradical BRi is thus the source of the polarizations. It is formed in a triplet state, its singlet exit channel produces the oxolane Pi, and its triplet exit channel the oxetane P2. 

As opposed to the previous examples, the rate of the pair substitution BRi BR2 BR3 can be varied by neither the reactant concentrations nor the solvent polarity because it is intramolecular and only involves neutral species. However, the ratio of polarizations of corresponding protons in Pi and P2 exhibits a pronounced temperature dependence, " which is shown in Fig. 9.8 and can be explained in the following way. Ideally, these opposite polarizations should have exactly equal magnitudes, but their ratio deviates from 1 if nuclear spin relaxation in the paramagnetic intermediates is taken into account. Biradicals with nuclear spin states that slow down intersystem crossing of BRi live longer, so their nuclear spins suffer a stronger relaxation loss. 

Cd + reacts with 3,5-di-t-buthyl-l,2-o-benzoquinine to form a biradical compound which can add a neutral N-donor ligand (py or bipy) to give 1 1 and 1 2 adducts. 

BonaCiC-Kouteck, V., Kouteck, J., Michl, J. (1987), Neutral and Charged Biradicals, Zwitterions, Funnels in S, and Proton Translocation Their Role in Photochemistry, Photophysics and Vision, Angew. Chem. Int. Ed. Engl. 26, 170. 

Support for a free-radical mechanism for dextrinization is afforded by comparison of the processes conducted in air with those carried out under a neutral atmosphere and under vacuum. The absence of oxygen accelerates dextrinization, and thus, the overall process yielding dextrins is not merely oxidation furthermore, free radicals are trapped by molecular oxygen, a biradical. Pyrolysis of a-D-glucose at 300° to 1,4 3,6-dianhydro-f -D-... 

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