Base hydrolysis of mer-trispicolinatoruthenium(III)

Kinetics and mechanism

Olga Impert, Anna Katafias, Przemysław Kita, Grzegorz Wrzeszcz, Joanna Fenska, G. Lente, I. Fábián

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The mer-[Ru(pic)3] isomer, where pic is 2-pyridinecarboxylic acid, undergoes base hydrolysis at pH > 12. The reaction was monitored spectrophotometrically within the UV-Vis spectral range. The product of the reaction, the [Ru(pic)2(OH)2]- ion, is formed via a consecutive two-stage process. The chelate ring opening is proceeded by the nucleophilic attack of OH- ion at the carbon atom of the carboxylic group and the deprotonation of the attached hydroxo group. In the second stage, the fast deprotonation of the coordinated OH- ligand leads to liberation of the monodentato bonded picolinate. The dependence of the observed pseudo-first-order rate constant on [OH-] is given by k kobs1=k+k1[OH-]+k+k2k 1[OH-]2/ k-+k1+(k ++k2K1[OH-]+kkk 1[OH-]2 and (kkobs2 = k ca+kcbk2[OH-]/1+k 2[OH-] for the first and the second stage, respectively, where k 1, k 2, k -, k ca, k cb are the first-order rate constants and k + is the second-order one, K 1 and K 2 are the protolytic equilibria constants.

Original languageEnglish
Pages (from-to)761-766
Number of pages6
JournalTransition Metal Chemistry
Volume36
Issue number7
DOIs
Publication statusPublished - Oct 2011

Fingerprint

Deprotonation
Hydrolysis
Rate constants
Kinetics
Equilibrium constants
Ions
Isomers
Ligands
Atoms
Carbon
Acids
hydroxide ion

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Materials Chemistry
  • Metals and Alloys

Cite this

Base hydrolysis of mer-trispicolinatoruthenium(III) : Kinetics and mechanism. / Impert, Olga; Katafias, Anna; Kita, Przemysław; Wrzeszcz, Grzegorz; Fenska, Joanna; Lente, G.; Fábián, I.

In: Transition Metal Chemistry, Vol. 36, No. 7, 10.2011, p. 761-766.

Research output: Contribution to journalArticle

Impert, Olga ; Katafias, Anna ; Kita, Przemysław ; Wrzeszcz, Grzegorz ; Fenska, Joanna ; Lente, G. ; Fábián, I. / Base hydrolysis of mer-trispicolinatoruthenium(III) : Kinetics and mechanism. In: Transition Metal Chemistry. 2011 ; Vol. 36, No. 7. pp. 761-766.
@article{297a2a688e3e4c2b9271e823633cfd20,
title = "Base hydrolysis of mer-trispicolinatoruthenium(III): Kinetics and mechanism",
abstract = "The mer-[Ru(pic)3] isomer, where pic is 2-pyridinecarboxylic acid, undergoes base hydrolysis at pH > 12. The reaction was monitored spectrophotometrically within the UV-Vis spectral range. The product of the reaction, the [Ru(pic)2(OH)2]- ion, is formed via a consecutive two-stage process. The chelate ring opening is proceeded by the nucleophilic attack of OH- ion at the carbon atom of the carboxylic group and the deprotonation of the attached hydroxo group. In the second stage, the fast deprotonation of the coordinated OH- ligand leads to liberation of the monodentato bonded picolinate. The dependence of the observed pseudo-first-order rate constant on [OH-] is given by k kobs1=k+k1[OH-]+k+k2k 1[OH-]2/ k-+k1+(k ++k2K1[OH-]+kkk 1[OH-]2 and (kkobs2 = k ca+kcbk2[OH-]/1+k 2[OH-] for the first and the second stage, respectively, where k 1, k 2, k -, k ca, k cb are the first-order rate constants and k + is the second-order one, K 1 and K 2 are the protolytic equilibria constants.",
author = "Olga Impert and Anna Katafias and Przemysław Kita and Grzegorz Wrzeszcz and Joanna Fenska and G. Lente and I. F{\'a}bi{\'a}n",
year = "2011",
month = "10",
doi = "10.1007/s11243-011-9530-y",
language = "English",
volume = "36",
pages = "761--766",
journal = "Transition Metal Chemistry",
issn = "0340-4285",
publisher = "Springer Netherlands",
number = "7",

}

TY - JOUR

T1 - Base hydrolysis of mer-trispicolinatoruthenium(III)

T2 - Kinetics and mechanism

AU - Impert, Olga

AU - Katafias, Anna

AU - Kita, Przemysław

AU - Wrzeszcz, Grzegorz

AU - Fenska, Joanna

AU - Lente, G.

AU - Fábián, I.

PY - 2011/10

Y1 - 2011/10

N2 - The mer-[Ru(pic)3] isomer, where pic is 2-pyridinecarboxylic acid, undergoes base hydrolysis at pH > 12. The reaction was monitored spectrophotometrically within the UV-Vis spectral range. The product of the reaction, the [Ru(pic)2(OH)2]- ion, is formed via a consecutive two-stage process. The chelate ring opening is proceeded by the nucleophilic attack of OH- ion at the carbon atom of the carboxylic group and the deprotonation of the attached hydroxo group. In the second stage, the fast deprotonation of the coordinated OH- ligand leads to liberation of the monodentato bonded picolinate. The dependence of the observed pseudo-first-order rate constant on [OH-] is given by k kobs1=k+k1[OH-]+k+k2k 1[OH-]2/ k-+k1+(k ++k2K1[OH-]+kkk 1[OH-]2 and (kkobs2 = k ca+kcbk2[OH-]/1+k 2[OH-] for the first and the second stage, respectively, where k 1, k 2, k -, k ca, k cb are the first-order rate constants and k + is the second-order one, K 1 and K 2 are the protolytic equilibria constants.

AB - The mer-[Ru(pic)3] isomer, where pic is 2-pyridinecarboxylic acid, undergoes base hydrolysis at pH > 12. The reaction was monitored spectrophotometrically within the UV-Vis spectral range. The product of the reaction, the [Ru(pic)2(OH)2]- ion, is formed via a consecutive two-stage process. The chelate ring opening is proceeded by the nucleophilic attack of OH- ion at the carbon atom of the carboxylic group and the deprotonation of the attached hydroxo group. In the second stage, the fast deprotonation of the coordinated OH- ligand leads to liberation of the monodentato bonded picolinate. The dependence of the observed pseudo-first-order rate constant on [OH-] is given by k kobs1=k+k1[OH-]+k+k2k 1[OH-]2/ k-+k1+(k ++k2K1[OH-]+kkk 1[OH-]2 and (kkobs2 = k ca+kcbk2[OH-]/1+k 2[OH-] for the first and the second stage, respectively, where k 1, k 2, k -, k ca, k cb are the first-order rate constants and k + is the second-order one, K 1 and K 2 are the protolytic equilibria constants.

UR - http://www.scopus.com/inward/record.url?scp=80053570804&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=80053570804&partnerID=8YFLogxK

U2 - 10.1007/s11243-011-9530-y

DO - 10.1007/s11243-011-9530-y

M3 - Article

VL - 36

SP - 761

EP - 766

JO - Transition Metal Chemistry

JF - Transition Metal Chemistry

SN - 0340-4285

IS - 7

ER -