Original Articles
Khaleel A. Abu-Sbeih and Tareq
Abstract
Organic chemistry transformations mediated by transition metals is one of the active and hot inter-disciplinary research topics. ACS/CODH is an important enzyme that catalyzes the formation of acetyl CoA from CO2 and CH3. The mechanism by which ACS catalyzes the formation of CH3CO-SCoA from CO and CH3 is studied theoretically using DFT and a new nickel model in which the metal is coordinated by three sulfur atoms. The analysis illustrates that the reaction course starts with CO binding to Ni(I) followed by CH3 binding to form a Ni(II) trigonal bipyramidal intermediate. Ultimately, migration results in the formation of an acetyl intermediate. This path is supported by structural parameters comparable to literature values. The details are new addition to nickel(I) chemistry and allow designing new coordination environment and catalyst models for fine-tuning characteristics of the transformation process.