A thiocarbonate sink on the enzymatic energy landscape of aerobic CO oxidation? Answers from DFT and QM/MM models of Mo–Cu CO-dehydrogenases

Research output: Contribution to journalArticle


We present a theoretical investigation providing key insights on a long-standing controversial issue that dominated the debate on carbon monoxide oxidation by Mo–Cu CO-dehydrogenases. Previous investigations gravitate around the possible occurrence of a thiocarbonate intermediate, that was repeatedly reported to behave as a thermodynamic sink on the catalytic energy landscape. By using a hierarchy of quantum mechanical and hybrid quantum/classical models of the enzyme, we show that no such energy sink is present on the catalytic energy profile. Consequent perspectives for the definition of a novel mechanistic proposal for the enzyme-catalyzed CO-oxidation are discussed in light of the recent literature.


  • Anna Rovaletti
  • Maurizio Bruschi
  • Giorgio Moro
  • Ugo Cosentino
  • Ulf Ryde
  • Claudio Greco
External organisations
  • University of Milano-Bicocca
Research areas and keywords

Subject classification (UKÄ) – MANDATORY

  • Biocatalysis and Enzyme Technology
  • Theoretical Chemistry


  • Carbon monoxide, CO-dehydrogenase, Copper, DFT, Molybdenum, Thiocarbonate intermediate
Original languageEnglish
Pages (from-to)201-205
Number of pages5
JournalJournal of Catalysis
Publication statusPublished - 2019
Publication categoryResearch