Handling methane: a Ni(i) F430-like cofactor derived from VB12 is active in methyl-coenzyme M reductase

Abstract

Replacing coenzyme F₄₃₀, an Ni(I) F₄₃₀-like cofactor derived from vitamin B₁₂ (F_430-B12) is revealed by DFT calculations to be able to catalyze methane formation in methyl-coenzyme M reductase with a barrier of 13.3 kcal mol⁻¹, demonstrating the correctness of the route starting from vitamin B₁₂. The structure–activity relationships of F₄₃₀ and F_430-B12 (especially the roles of the F ring) are discovered and several sources of inspiration promoting the application of F_430-B12 are also obtained, coming closer to using F₄₃₀ chemistry in man-made catalysis.