Pt center dot center dot center dot H Nonclassical Interaction in Water-Dissolved Pt(II) Complexes: Coaction of Electronic Effects with Solvent-Assisted Stabilization

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60076658%3A12310%2F16%3A43890599" target="_blank" >RIV/60076658:12310/16:43890599 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60076658:12110/16:43890599

Výsledek na webu

<a href="http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b02261" target="_blank" >http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.5b02261</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.inorgchem.5b02261" target="_blank" >10.1021/acs.inorgchem.5b02261</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Pt center dot center dot center dot H Nonclassical Interaction in Water-Dissolved Pt(II) Complexes: Coaction of Electronic Effects with Solvent-Assisted Stabilization

Popis výsledku v původním jazyce

The structure of the hydration shell of cisplatin, cis[Pt(NH3)(2)Cl-2], and its aquated derivatives cis-[Pt(NH3)(2)Cl(H2O)](+), cis-[Pt(NH3)(2)OH(H2O)](+), and cis-[Pt(NH3)(2)(H2O)(2)](2+) were studied by a number of density functional molecular dynamics (DFT-MD) simulations (from 30 to 250 ps) in which Pt(II) complexes were immersed in a periodic box with 72 explicit water molecules. Furthermore, Pt(II) complex-water binding energy curves and full DFT optimizations of dusters derived from the lowest potential energy DFT-MD frames offered a deeper insight into the structure of the first hydration shell and electronic changes connected with the formation of a nonclassical Pt center dot center dot center dot H-O-H (Pt center dot center dot center dot Hw) hydrogen bond (inverse hydration). The probability of a Pt center dot center dot center dot Hw interaction decreases with increasing charge of the platinum complex due to disadvantageous electrostatics. The main stabilization comes from the charge transfer being followed by polarization and dispersion. Ligands form a framework for the network of H-bond interactions between the solvent molecules, which play an important role in the promotion/suppression of the formation of the Pt center dot center dot center dot Hw interactions. In the +2 charged diaqua complex the Pt center dot center dot center dot Hw interaction is still attractive but cannot compete with classical H bonds between solvent molecules. Thus, the formation of a Pt center dot center dot center dot Hw interaction is the result of a suitable solvent H-bonding network and the probability of its incidence decreases with increasing flexibility of the solvent.

Název v anglickém jazyce

Pt center dot center dot center dot H Nonclassical Interaction in Water-Dissolved Pt(II) Complexes: Coaction of Electronic Effects with Solvent-Assisted Stabilization

Popis výsledku anglicky

The structure of the hydration shell of cisplatin, cis[Pt(NH3)(2)Cl-2], and its aquated derivatives cis-[Pt(NH3)(2)Cl(H2O)](+), cis-[Pt(NH3)(2)OH(H2O)](+), and cis-[Pt(NH3)(2)(H2O)(2)](2+) were studied by a number of density functional molecular dynamics (DFT-MD) simulations (from 30 to 250 ps) in which Pt(II) complexes were immersed in a periodic box with 72 explicit water molecules. Furthermore, Pt(II) complex-water binding energy curves and full DFT optimizations of dusters derived from the lowest potential energy DFT-MD frames offered a deeper insight into the structure of the first hydration shell and electronic changes connected with the formation of a nonclassical Pt center dot center dot center dot H-O-H (Pt center dot center dot center dot Hw) hydrogen bond (inverse hydration). The probability of a Pt center dot center dot center dot Hw interaction decreases with increasing charge of the platinum complex due to disadvantageous electrostatics. The main stabilization comes from the charge transfer being followed by polarization and dispersion. Ligands form a framework for the network of H-bond interactions between the solvent molecules, which play an important role in the promotion/suppression of the formation of the Pt center dot center dot center dot Hw interactions. In the +2 charged diaqua complex the Pt center dot center dot center dot Hw interaction is still attractive but cannot compete with classical H bonds between solvent molecules. Thus, the formation of a Pt center dot center dot center dot Hw interaction is the result of a suitable solvent H-bonding network and the probability of its incidence decreases with increasing flexibility of the solvent.

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

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

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2016

Kód důvěrnosti údajů

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

Název periodika

Inorganic Chemistry

ISSN

0020-1669

e-ISSN

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Svazek periodika

55

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

3252-3264

Kód UT WoS článku

000373550700010

EID výsledku v databázi Scopus

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