Comprehensive Theoretical View of the [Cu2O2] Side-on-Peroxo-/Bis-μ-Oxo Equilibria

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F22%3A00557863" target="_blank" >RIV/61388963:_____/22:00557863 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/00216208:11310/22:10458325

Výsledek na webu

<a href="https://doi.org/10.1002/cphc.202200076" target="_blank" >https://doi.org/10.1002/cphc.202200076</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/cphc.202200076" target="_blank" >10.1002/cphc.202200076</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Comprehensive Theoretical View of the [Cu2O2] Side-on-Peroxo-/Bis-μ-Oxo Equilibria

Popis výsledku v původním jazyce

Coupled binuclear copper (CBC) sites are employed by many metalloenzymes to catalyze a broad set of biochemical transformations. Typically, the CBC catalytic sites are activated by the O-2 molecule to form various [Cu2O2] reactive species. This has also inspired synthesis and development of various biomimetic inorganic complexes featuring the CBC core. From theoretical perspective, the [Cu2O2] reactivity often hinges on the side-on-peroxo-dicopper(II) (P) vs. bis-mu-oxo-dicopper(III) (O) isomerism an equilibrium that has become almost iconic in theoretical bioinorganic chemistry. Herein, we present a comprehensive calibration and evaluation of the performance of various composite computational protocols available in contemporary computational chemistry, involving coupled-cluster and multireference (relativistic) wave function methods, popular density functionals and solvation models. Starting with the well-studied reference [Cu2O2(NH3)(6)](2+) system, we compared the performance of electronic structure methods and discussed the relativistic effects. This allowed us to select several 'calibrated' DFT functionals that can be conveniently employed to study ten experimentally well-characterized [Cu2O2] inorganic systems. We mostly predicted the lowest-energy structures (P vs. O) of the studied systems correctly. In addition, we present calibration of the used electronic structure methods for prediction of the spectroscopic features of the [Cu2O2] core, mostly provided by the resonance Raman (rR) spectroscopy.

Název v anglickém jazyce

Comprehensive Theoretical View of the [Cu2O2] Side-on-Peroxo-/Bis-μ-Oxo Equilibria

Popis výsledku anglicky

Coupled binuclear copper (CBC) sites are employed by many metalloenzymes to catalyze a broad set of biochemical transformations. Typically, the CBC catalytic sites are activated by the O-2 molecule to form various [Cu2O2] reactive species. This has also inspired synthesis and development of various biomimetic inorganic complexes featuring the CBC core. From theoretical perspective, the [Cu2O2] reactivity often hinges on the side-on-peroxo-dicopper(II) (P) vs. bis-mu-oxo-dicopper(III) (O) isomerism an equilibrium that has become almost iconic in theoretical bioinorganic chemistry. Herein, we present a comprehensive calibration and evaluation of the performance of various composite computational protocols available in contemporary computational chemistry, involving coupled-cluster and multireference (relativistic) wave function methods, popular density functionals and solvation models. Starting with the well-studied reference [Cu2O2(NH3)(6)](2+) system, we compared the performance of electronic structure methods and discussed the relativistic effects. This allowed us to select several 'calibrated' DFT functionals that can be conveniently employed to study ten experimentally well-characterized [Cu2O2] inorganic systems. We mostly predicted the lowest-energy structures (P vs. O) of the studied systems correctly. In addition, we present calibration of the used electronic structure methods for prediction of the spectroscopic features of the [Cu2O2] core, mostly provided by the resonance Raman (rR) spectroscopy.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ChemPhysChem

ISSN

1439-4235

e-ISSN

1439-7641

Svazek periodika

23

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

15

Strana od-do

e202200076

Kód UT WoS článku

000799503600001

EID výsledku v databázi Scopus

2-s2.0-85130450646