Spectroscopic and DFT Study of RhIII Chloro
Complex Transformation in Alkaline Solutions
Posted on 2017-08-21 - 18:37
The hydrolysis of [RhCl6]3– in NaOH–water solutions was studied
by spectrophotometric methods. The reaction proceeds via successive
substitution of chloride with hydroxide to quantitatively form [Rh(OH)6]3–. Ligand substitution kinetics was studied
in an aqueous 0.434–1.085 M NaOH matrix in the temperature
range 5.5–15.3 °C. Transformation of [RhCl6]3– into [RhCl5(OH)]3– was found to be the rate-determining step with activation parameters
of ΔH† = 105 ± 4 kJ
mol–1 and ΔS†= 59 ± 10 J K–1 mol–1. The
coordinated hydroxo ligand(s) induces rapid ligand substitution to
form [Rh(OH)6]3–. By simulating ligand
substitution as a dissociative mechanism, using density functional
theory (DFT), we can now explain the relatively fast and slow kinetics
of chloride substitution in basic and acidic matrices, respectively.
Moreover, the DFT calculated activation energies corroborated experimental
data that the kinetic stereochemical sequence of [RhCl6]3– hydrolysis in an acidic solution proceeds as
[RhCl6]3– → [RhCl5(H2O)]2– → cis-[RhCl4(H2O)2]−. However,
DFT calculations predict in a basic solution the trans route of substitution
[RhCl6]3– → [RhCl5(OH)]3– → trans-[RhCl4(OH)2]3– is kinetically favored.
CITE THIS COLLECTION
DataCite
3 Biotech
3D Printing in Medicine
3D Research
3D-Printed Materials and Systems
4OR
AAPG Bulletin
AAPS Open
AAPS PharmSciTech
Abhandlungen aus dem Mathematischen Seminar der Universität Hamburg
ABI Technik (German)
Academic Medicine
Academic Pediatrics
Academic Psychiatry
Academic Questions
Academy of Management Discoveries
Academy of Management Journal
Academy of Management Learning and Education
Academy of Management Perspectives
Academy of Management Proceedings
Academy of Management Review
Vasilchenko, Danila B.; Berdyugin, Semen N.; Korenev, Sergey V.; O’Kennedy, Sean; Gerber, Wilhelmus J. (2017). Spectroscopic and DFT Study of RhIII Chloro
Complex Transformation in Alkaline Solutions. ACS Publications. Collection. https://doi.org/10.1021/acs.inorgchem.7b01672
or
Select your citation style and then place your mouse over the citation text to select it.
SHARE
Usage metrics
Read the peer-reviewed publication
AUTHORS (5)
DV
Danila B. Vasilchenko
SB
Semen N. Berdyugin
SK
Sergey V. Korenev
SO
Sean O’Kennedy
WG
Wilhelmus J. Gerber