Issue 27, 2024

Delving into the catalytic mechanism of molybdenum cofactors: a novel coupled cluster study

Abstract

In this work, we use modern electronic structure methods to model the catalytic mechanism of different variants of the molybdenum cofactor (Moco). We investigate the dependence of various Moco model systems on structural relaxation and the importance of environmental effects for five critical points along the reaction coordinate with the DMSO and NO3 substrates. Furthermore, we scrutinize the performance of various coupled-cluster approaches for modeling the relative energies along the investigated reaction paths, focusing on several pair coupled cluster doubles (pCCD) flavors and conventional coupled cluster approximations. Moreover, we elucidate the Mo–O bond formation using orbital-based quantum information measures, which highlight the flow of σM–O bond formation and σN/S–O bond breaking. Our study shows that pCCD-based models are a viable alternative to conventional methods and offer us unique insights into the bonding situation along a reaction coordinate. Finally, this work highlights the importance of environmental effects or changes in the core and, consequently, in the model itself to elucidate the change in activity of different Moco variants.

Graphical abstract: Delving into the catalytic mechanism of molybdenum cofactors: a novel coupled cluster study

Supplementary files

Article information

Article type
Paper
Submitted
11 4 2024
Accepted
20 6 2024
First published
20 6 2024

Phys. Chem. Chem. Phys., 2024,26, 18918-18929

Delving into the catalytic mechanism of molybdenum cofactors: a novel coupled cluster study

M. Gałyńska, M. M. F. de Moraes, P. Tecmer and K. Boguslawski, Phys. Chem. Chem. Phys., 2024, 26, 18918 DOI: 10.1039/D4CP01500B

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