Syntheses of Ir3MS4 (M = Ru, Fe) Cubane-type Sulfido Clusters and Their Reactions with Small Molecules

摘要

Nitrogenase can catalyze the reduction of quite inert N2 molecule into ammonia under ambient conditions. Since the structure of the active site (FeMo-co) has been crystallographically revealed to have an MoFe7S9X core in the case of Mo-containing nitrogenase, transition metal-sulfido clusters can be promising catalysts for new industrial N2-fixing system that operate under mild conditions. However, it is yet uncertain where and how the N2 molecule is converted into ammonia in FeMo-co, and besides, any metal sulfido clusters with N2 ligand are unprecedented. To develop synthetic models of FeMo-co, our studies have focused on cubane-type sulfido clusters because their core structure is the fundamental framework that can be found as the partial structure in FeMo-co. Here we report syntheses of Ir3MS4 (M = Ru, Fe) cubane-type clusters, in which Group 8 metal centers become the accessible site for molecular N2 as well as other small molecules relevant to nitrogenase.