Impact of dielectric constant of solvent on the formation of transition metal-ammine complexes

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388963%3A_____%2F24%3A00576277" target="_blank" >RIV/61388963:_____/24:00576277 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61989592:15640/24:73621737 RIV/61989100:27740/24:10253094

Výsledek na webu

<a href="https://doi.org/10.1002/jcc.27230" target="_blank" >https://doi.org/10.1002/jcc.27230</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/jcc.27230" target="_blank" >10.1002/jcc.27230</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Impact of dielectric constant of solvent on the formation of transition metal-ammine complexes

Popis výsledku v původním jazyce

The DFT-level computational investigations into Gibbs free energies (ΔG) demonstrate that as the dielectric constant of the solvent increases, the stabilities of [M(NH3)n]2+/3+ (n = 4, 6, M = selected 3d transition metals) complexes decrease. However, there is no observed correlation between the stability of the complex and the solvent donor number. Analysis of the charge transfer and Wiberg bond indices indicates a dative-bond character in all the complexes. The solvent effect assessed through solvation energy is determined by the change in the solvent accessible surface area (SASA) and the change in the charge distribution that occurs during complex formation. It has been observed that the SASA and charge transfer are different in the different coordination numbers, resulting in a variation in the solvent effect on complex stability in different solvents. This ultimately leads to a change between the relative stability of complexes with different coordination numbers while increasing the solvent polarity for a few complexes. Moreover, the findings indicate a direct relationship between ΔΔG (∆Gsolvent-∆Ggas) and ΔEsolv, which enables the computation of ΔG for the compounds in a particular solvent using only ΔGgas and ΔEsolv. This approach is less computationally expensive.

Název v anglickém jazyce

Impact of dielectric constant of solvent on the formation of transition metal-ammine complexes

Popis výsledku anglicky

The DFT-level computational investigations into Gibbs free energies (ΔG) demonstrate that as the dielectric constant of the solvent increases, the stabilities of [M(NH3)n]2+/3+ (n = 4, 6, M = selected 3d transition metals) complexes decrease. However, there is no observed correlation between the stability of the complex and the solvent donor number. Analysis of the charge transfer and Wiberg bond indices indicates a dative-bond character in all the complexes. The solvent effect assessed through solvation energy is determined by the change in the solvent accessible surface area (SASA) and the change in the charge distribution that occurs during complex formation. It has been observed that the SASA and charge transfer are different in the different coordination numbers, resulting in a variation in the solvent effect on complex stability in different solvents. This ultimately leads to a change between the relative stability of complexes with different coordination numbers while increasing the solvent polarity for a few complexes. Moreover, the findings indicate a direct relationship between ΔΔG (∆Gsolvent-∆Ggas) and ΔEsolv, which enables the computation of ΔG for the compounds in a particular solvent using only ΔGgas and ΔEsolv. This approach is less computationally expensive.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GX19-27454X" target="_blank" >GX19-27454X: Ovlivnění elektronických vlastností organometalických molekul pomocí jejich nekovalentních interakcí s rozpouštědly, ligandy a 2D nanosystémy</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Journal of Computational Chemistry

ISSN

0192-8651

e-ISSN

1096-987X

Svazek periodika

45

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

6

Strana od-do

204-209

Kód UT WoS článku

001070770000001

EID výsledku v databázi Scopus

2-s2.0-85172667457