Organo-transition metal complexes typically refer to compounds possessing transition metal-carbon bonds or interactions, while the term sometimes indicates their precursors. These organometallic compounds are generally susceptible to hydrolysis and react readily with oxygen, making most of them incompatible with biological environments. However, and interestingly, some transition metal complexes in proteins can be categorized as organometallic compounds, especially those found as the active sites of enzymes responsible for reduction reactions. They feature metal-sulfur cluster cores composed of multiple metal and sulfur atoms. A notable example is the active site of N2-reducing enzyme (i.e. FeMo-cofactor of Nitrogenase), which features a central carbon atom bridging six iron atoms. The structure of FeMo-cofactor is quite complicated, and thereby even after its structural elucidation, it remains difficult to clarify the relationship between its structure and function (reactivity). In this study, we designed and synthesized molybdenum-containing cubic metal-sulfur clusters for the activation of N2. Some notable achievements include the synthesis of a series of cubic [Mo3S4M] clusters with a specific reaction site M (M = 1st row transition elements),1,2 their application in the stoichiometric activation of N23, and catalytic silylation of N2.4,5
(1) Chem. Eur. J. 2018, 24, 17138.
(2) Inorg. Chem. 2019, 58, 5230.
(3) Nat. Commun. 2018, 9, 3200.
(4) Nature 2022, 607, 86.
(5) Coord. Chem. Res. 2024, 1, 100001