Kinetics and mechanism of the reaction of tetracobalt dodecacarbonyl with carbon monoxide under pressure

The kinetics of the reaction of tetracobalt dodecacarbonyl with carbon monoxide to form dicobalt octacarbonyl in n-hexane have been investigated over a wide range of temperature and CO pressure. The reaction is first order in [Co₄(CO)₁₂]; the order in [CO] changes between one (at low pressures and high temperatures) and two (at high pressures and low temperatures).Activation parameters have been estimated and a mechanism involving initial reversible breaking of one CoCo bond, followed by irreversible breaking of a second, is proposed. The first step involves concerted addition of CO while the second can proceed with or without such addition.