Abiological nitrogen fixation using homogeneous catalysts
Abiological nitrogen fixation describes chemical processes that fix (react with) N2, usually with the goal of generating ammonia. The dominant technology for abiological nitrogen fixation is the Haber process, which uses an iron-based heterogeneous catalysts and H2 to convert N2 to NH3. This article focuses on homogeneous (soluble) catalysts for the same or similar conversions. Transition metals Vol'pin and Shur An early influential discovery of abiological nitrogen fixation was made by Vol'pin and co-workers in Russia in 1970. Aspects are described in an early review: "using a non-protic Lewis acid, aluminium tribromide, were able to demonstrate the truly catalytic effect of titanium by treating dinitrogen with a mixture of titanium tetrachloride, metallic aluminium, and aluminium tribromide at 50 °C, either in the absence or in the presence of a solvent, e.g. benzene. As much as 200 mol of ammonia per mol of was obtained after hydrolysis.…" These results led to many studies on dinitrogen complexes of titanium and zirconium. Mo- and Fe-based systems Because Mo and Fe are found at the active site of the most common and most active form of nitrogenase, these metals have been the focus of particular attention for homogeneous catalysis. Most catalytic systems operate according