CRC 235 Emergence of Life

Breadcrumb Navigation


Mackinawite supported reduction of C1 substrates into prebiotically relevant precursors

M. Grosch 2022 ChemSystemsChem


Mario Grosch, Martin T Stiebritz, Robert Bolney, Mario Winkler, Eric Jückstock, Hannah Busch, Sophia Peters, Alexander F. Siegle, Joris van Slageren, Markus Ribbe, Yilin Hu, Oliver Trapp, Christian Robl, Wolfgang Weigand



Mackinawite has unique structural properties and reactivities when compared to other iron sulfides. Here we provide evidence for the mackinawite-supported reduction of KCN into various reduced compounds under primordial conditions. A reaction mechanism is proposed based on the nucleophilic attack by the deprotonated mackinawite -SH surface groups at the carbon atom of HCN. The initial binding of substrate and the subsequent reduction events are supported by DFT calculations and further experiments using other substrates, such as KSCN, KOCN and CS2. Until now, conversion of CN- into CH4 and NH3 has been limited to nitrogenase cofactors or molecular Fe-CN complexes. Our study provides evidence for mackinawite-supported cleavage of the C-N bond under ambient conditions, which opens new avenues for investigation of other substrates for mackinawite-supported reactions while shedding lights on the relevance of this type of reaction to the origin of life on Earth.