Oxygen atom singlet

Acetylene is oxidized to ketene by hot air (24JCS(125)1534). Oxirene is probably not involved since molecular oxygen is not a donor of singlet oxygen atoms (see the remarks on this point in (64JA4866)). 

Hence either the reactive singlet oxygen molecule or oxygen atoms are produced either of these may initiate radical chain processes that lead to degradation. 

Such an orbital phase picture in Fig. 14 is also applicable to rationalize the relative S-T gaps of hetero diradicals 19 and 20. hi comparison with their parent system, 1,3-dimethylenecyclobutadiene (DMCBD, 10), the introduction of oxygen atoms does destabilize the triplet state. The calculated energy gap between singlet and triplet states, AE deaeases in the order 10 (18.2 kcal moF ) > 19 (7.7 kcal moF ) > 20 (-20.7 kcal moF ) [64]. These results supported the orbital phase predictions. 

Methanal (formol) presents an additional degree of freedom the out-of-plane wagging of the oxygen atom. In its singlet ground, X Ai, this molecule is planar. But, in its triplet and singlet lowest exited W A" and tt ), this molecule is pyramidal... 

This conclusion is in agreement with experiments in which a smootb quartz and cellulose were used as substrates. For above materials the transfer of excitation energy of the dye into the substrate is low which is confirmed by intensive luminescence of adsorbed tripaflavine. Note, that the activation energy of emission of singlet oxygen is close for zinc oxide oxidized by oxygen atoms, quartz and cellulose and amounts to 5-10 kcal/mol [83]. 

Thus we end up with an oxygen atom which is somewhat electron deficient and a carbon atom which is electron rich. The oxygen then would be expected to behave as an electrophilic reagent and the carbon (or rather the regions bounded by the w orbital) should behave as a nucleophilic reagent. The amphoteric nature of the carbonyl n- n singlet state is mirrored in its reactivity toward electron-rich and electron-deficient olefins. 

An investigation148 of 1849 A photolysis of aqueous N20 has shown that not more than 10 % of quanta absorbed by N20 in solution gives other than singlet oxygen atoms. This result conflicts with the gas-phase data147. 

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