On the Synthesis of the FeMo Cofactor of Nitrogenase: Gene‐Controlled in Nature versus Laboratory‐Produced by Man

Abstract

One of the primary challenges of chemistry is the controlled synthesis of compounds with tailor‐made structures and properties. Natural products serve as inspiration in this quest, ranging from biocatalysts with optimal selectivity and activity to “inorganic materials” with exceptional properties, whose generation can be described by the term biomineralization. It is of fundamental importance to comprehend the courses of events at the interface between gene expression and the subsequent processes of epigenesis that are no longer under gene control. Chemistry has been able to achieve many goals; however, in the area of controlled syntheses of highly complex, tailor‐made metal clusters, there is a lack of fundamental theories and principles. This is especially true for the fascinating metal–sulfur cluster of nitrogenase, which, in this enzyme, functions as the active center for the N2 reduction and, so far, has eluded all attempts to be synthesized in the laboratory. To understand the biosynthesis of this cluster, information from genetics and chemistry must be combined.

Unusual Stepwise Assembly and Molecular Growth: [H14Mo37O112]14− and [H3Mo57V6(NO)6O189(H2O)12(MoO)6]21−

“…The FeMo cofactor of the FeMo-protein nitrogenase for instanceÐan unusual hetero metal ± sulfur cluster important for the development and existence of life on EarthÐis generated stepwise with the help of various genes. [24] In this context, however, we also have to address the basic question of whether it is possible to create molecular complexity, not only far from equilibrium as in the biosphere, but also under near-equilibrium conditions, by some conservative growth process (Scheme 2) including feedback 4 , respectively, which was not originally abundant in solution. The complex system at the end of the growth process is generated by a symmetry-breaking step (see also ref.…”

New Developments in Nitrogen Fixation

“…So far, the iron ± molybdenum cofactor (FeMoco), which is the center of bonding and reduction of dinitrogen in the enzyme nitrogenase, [1] has not been synthesized. [2] Furthermore, this cofactor does not bind N 2 in isolated form. It therefore appears more promising to realize a catalytic cycle based on the mono-and binuclear transition metal N 2 compounds that give NH 3 or N 2 H 4 upon protonation.…”

Heterometallic transition metal clusters and cluster-supported coordination polymers derived from Tp- and Tp*-based Mo(W) sulfido precursors

“…The two Cu centers in each of the butterfly-shaped cluster cores adopt trigonal planar and tetrahedral coordination modes, respectively. Apart from being associated with two -S atoms for each Cu, the trigonal planar coordination is completed by one additional N py association, while the tetrahedral coordination is completed by one N py and one additional N SCN (14) or S SCN (15) coordination (Fig. 4).…”

“…Müller [11][12][13][14], Sécheresse [15][16][17][18], Wu [19][20][21][22][23][24][25][26][27] and Xin [28][29][30][31] pioneered the work on the heterometallic Mo(W)-M-S (M = Fe, Cu, Ni, Ag, Au, etc.) clusters since 1980s, using [Mo(W)O x S 4−x ] 2− (x = 0, 1, 2) anions as precursors.…”