Thermal inner-sphere process

Other alternatives with 03 must be considered for T oxidation, including a possible thermal inner-sphere process. As with peroxide, 03 has an empty antibonding orbital. This ir-like orbital can accept electrons better than 02 and peroxide (lower ELUMO in Table II). Figure 5 shows the geometric arrangement of I" with 03. 

Romanian scientists compared one-electron transfer reactions from triphenylmethyl or 2-methyl benzoyl chloride to nitrobenzene in thermal (210°C) conditions and on ultrasonic stimulation at 50°C (lancu et al. 1992, Vinatoru et al. 1994, Chivu et al. 2006). In the first step, the chloride cation-radical and the nitrobenzene anion-radicals are formed. In the thermal and acoustic variants, the reactions lead to the same set of products with one important exception The thermal reaction results in the formation of HCl, whereas ultrasonic stimulation results in CI2 evolution. At present, it is difficult to elucidate the mechanisms behind these two reactions. As an important conclusion, the sonochemical process goes through the inner-sphere electron transfer. The outer-sphere electron transfer mechanism is operative in the thermally induced process. 

Thiolate sulfur in [Co(cyst)(en)2]2+ can be protonated in strong add without dissotiation from the metal1039 but all thiolate chelates seem to be unstable in strongly alkaline solutions undergoing slow thermal reduction via an inner-sphere electron-transfer process (equation 160).1056... 

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