[1] Chemistry of dioxygen

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The chemistry of molecular oxygen, or dioxygen as it is increasingly coming to be called, is dominated by the relative reluctance with which the element reacts with most, but not all, compounds. This quality is rarely thermodynamic in origin; rather the slow rate of reaction is associated with either the strong oxygen–oxygen bond or the character of the ground state of dioxygen or both. If a reaction is to take place with dioxygen in its ground state, there must be a change of spin at some stage during the reaction. This is forbidden, within the limitations of the descriptions used; at the very least, the reactions are improbable. For dioxygen to react rapidly, this spin restriction should be removed or the oxygen–oxygen bond should be partially weakened or both of these should occur simultaneously. It is not surprising that much of the chemistry of dioxygen is concerned with reactions with paramagnetic species, with electron-donating species, with light, or with various combinations of these three factors. This chapter discusses the chemistry of the reduction products of dioxygen, but one should be aware of the marked influence of all of these factors on most reactions of dioxygen. They are often, if not always, responsible for the promotion or catalysis of oxidation reactions.

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