Application of low-temperature rapid-scan techniques in the elucidation of inorganic reaction mechanisms

Reactions that occur too rapidly to be monitored by rapid reaction methods at temperatures at or close to ambient can be investigated kinetically by retarding their reaction rates employing very low temperatures. A selection of reactions studied by this approach (low-temperature stopped-flow spectrophotometry) is reported. Details of the reaction mechanisms have been revealed for peroxide activation involving iron(III) porphyrins and cytochrome P450, superoxide activation involving manganese(II) complexes and iron porphyrin complexes, and dioxygen activation and binding by model mono-, and dinuclear copper(I) complexes and dioxygen activation at mono-, and dinuclear non-heme iron complexes. A final section covers progress in unravelling the mechanism of carbon–hydrogen bond activation by platinum complexes.