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

Result code in 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>

Alternative codes found

RIV/60076658:12310/20:43901380

Result on the web

<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>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

—

Czech description

—

Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA16-06240S" target="_blank" >GA16-06240S: Structure and dynamics of organometallic complexes in bio-environment.</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2020

Confidentiality

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

Name of the periodical

ACS Omega

ISSN

2470-1343

e-ISSN

—

Volume of the periodical

5

Issue of the periodical within the volume

20

Country of publishing house

US - UNITED STATES

Number of pages

16

Pages from-to

11768-11783

UT code for WoS article

000537629600057

EID of the result in the Scopus database

2-s2.0-85085661937