Tuning the Reactivity and Bonding Properties of Metal Square-Planar Complexes by the Substitution(s) on the Trans-Coordinated Pyridine Ring

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60076658%3A12110%2F20%3A43901380" target="_blank" >RIV/60076658:12110/20:43901380 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/60076658:12310/20:43901380

Výsledek na webu

<a href="https://pubs.acs.org/doi/pdf/10.1021/acsomega.0c01161" target="_blank" >https://pubs.acs.org/doi/pdf/10.1021/acsomega.0c01161</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acsomega.0c01161" target="_blank" >10.1021/acsomega.0c01161</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Tuning the Reactivity and Bonding Properties of Metal Square-Planar Complexes by the Substitution(s) on the Trans-Coordinated Pyridine Ring

Popis výsledku v původním jazyce

The kinetics of the hydration reaction on trans-[Pt(NH3)(2)(pyrX)Cl](+) (pyr = pyridine) complexes (X = OH, Cl, F, Br, NO2, NH2, SH, CH3, C CH, and DMA) was studied by density functional theory calculations in the gas phase and in water solution described by the implicit polarizable continuum model method. All possible positions ortho, meta, and para of the substituent X in the pyridine ring were considered. The substitution of the pyr ligand by electron-donating X&apos;s led to the strengthening of the Pt-N1(pyrX) (Pt-N-pyrX) bond and the weakening of the trans Pt-Cl or Pt-O-w bonds. The electron-withdrawing X&apos;s have exactly the opposite effect. The strengths of these bonds can be predicted from the basicity of sigma electrons on the N-pyrX atom determined on the isolated pyrX ligand. As the pyrX ring was oriented perpendicularly with respect to the plane of the complex, the nature of the X center dot center dot center dot Cl electrostatic interaction was the decisive factor for the transition-state (TS) stabilization which resulted in the highest selectivity of ortho-substituted systems with respect to the reaction rate. Because of a smaller size of X&apos;s, the steric effects influenced less importantly the values of activation Gibbs energies Delta G(double dagger) but caused geometry changes such as the elongation of the Pt-NpyrX bonds. Substitution in the meta position led to the highest Delta G(double dagger) values for most of the X&apos;s. The changes of Delta G(double dagger) because of electronic effects were the same in the gas phase and the water solvent. However, as the water solvent dampened electrostatic interactions, 2200 and 150 times differences in the reaction rate were observed between the most and the least reactive mono-substituted complexes in the gas phase and the water solvent, respectively. An additional NO2 substitution of the pyrNO(2) ligand further decelerated the rate of the hydration reaction, but on the other hand, the poly-NH2 complexes were no more reactive than the fastest o-NH2 system. In the gas phase, the poly-X complexes showed the additivity of the substituent effects with respect to the Pt-ligand bond strengths and the ligand charges.

Název v anglickém jazyce

Tuning the Reactivity and Bonding Properties of Metal Square-Planar Complexes by the Substitution(s) on the Trans-Coordinated Pyridine Ring

Popis výsledku anglicky

The kinetics of the hydration reaction on trans-[Pt(NH3)(2)(pyrX)Cl](+) (pyr = pyridine) complexes (X = OH, Cl, F, Br, NO2, NH2, SH, CH3, C CH, and DMA) was studied by density functional theory calculations in the gas phase and in water solution described by the implicit polarizable continuum model method. All possible positions ortho, meta, and para of the substituent X in the pyridine ring were considered. The substitution of the pyr ligand by electron-donating X&apos;s led to the strengthening of the Pt-N1(pyrX) (Pt-N-pyrX) bond and the weakening of the trans Pt-Cl or Pt-O-w bonds. The electron-withdrawing X&apos;s have exactly the opposite effect. The strengths of these bonds can be predicted from the basicity of sigma electrons on the N-pyrX atom determined on the isolated pyrX ligand. As the pyrX ring was oriented perpendicularly with respect to the plane of the complex, the nature of the X center dot center dot center dot Cl electrostatic interaction was the decisive factor for the transition-state (TS) stabilization which resulted in the highest selectivity of ortho-substituted systems with respect to the reaction rate. Because of a smaller size of X&apos;s, the steric effects influenced less importantly the values of activation Gibbs energies Delta G(double dagger) but caused geometry changes such as the elongation of the Pt-NpyrX bonds. Substitution in the meta position led to the highest Delta G(double dagger) values for most of the X&apos;s. The changes of Delta G(double dagger) because of electronic effects were the same in the gas phase and the water solvent. However, as the water solvent dampened electrostatic interactions, 2200 and 150 times differences in the reaction rate were observed between the most and the least reactive mono-substituted complexes in the gas phase and the water solvent, respectively. An additional NO2 substitution of the pyrNO(2) ligand further decelerated the rate of the hydration reaction, but on the other hand, the poly-NH2 complexes were no more reactive than the fastest o-NH2 system. In the gas phase, the poly-X complexes showed the additivity of the substituent effects with respect to the Pt-ligand bond strengths and the ligand charges.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GA16-06240S" target="_blank" >GA16-06240S: Struktura a dynamika organokovových komplexů v biologickém prostředí.</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2020

Kód důvěrnosti údajů

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

Název periodika

ACS Omega

ISSN

2470-1343

e-ISSN

—

Svazek periodika

5

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

16

Strana od-do

11768-11783

Kód UT WoS článku

000537629600057

EID výsledku v databázi Scopus

2-s2.0-85085661937