Oxidation of Ru(III)-Bound Thiocyanate with Peroxomonosulfate: Kinetic and Mechanistic Studies

被引：1

作者：

Sarkar, Papiya ^{[1
]}

Chatterjee, Debabrata ^{[1
]}

机构：

[1] CSIR Cent Mech Engn Res Inst, Chem & Biomimet Grp, Durgapur 713209, India

来源：

INTERNATIONAL JOURNAL OF CHEMICAL KINETICS | 2016年 / 48卷 / 03期

关键词：

ETHYLENEDIAMINETETRAACETATE COMPLEXES; AQUEOUS-SOLUTION; H2O2; METALLOPHARMACEUTICALS; HYPOTHIOCYANITE; RUTHENIUM(III); REACTIVITIES;

D O I：

10.1002/kin.20976

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The reaction of [Ru-III(edta)(SCN)](2-) (edta(4-) = ethylenediaminetetraacetate; SCN- = thiocyanate ion) with the peroxomonosulfate ion (HSO5-) has been studied by using stopped-flow and rapid scan spectrophotometry as a function of [Ru-III(edta)], [HSO5-], and temperature (15-30oC) at constant pH 6.2 (phosphate buffer). Spectral analyses and kinetic data are suggestive of a pathway in which HSO5- effects the oxidation of the coordinated SCN- by its direct attack at the S-atom (of SCN-) coordinated to the Ru-III(edta). The high negative value of entropy of activation (S = -90 +/- 6 J mol(-1) deg(-1)) is consistent with the values reported for the oxygen atom transfer process involving heterolytic cleavage of the O-O bond in HSO5-. Formation of SO42-, SO32-, and OCN- was identified as oxidation products in ESI-MS experiments. A detailed mechanism in agreement with the spectral and kinetic data is presented.

引用

页码：117 / 123

页数：7

共 50 条

[11] Oxidation of diphenylcarbinols with bromamine-B in acid medium catalyzed by Ru(III), a kinetic and mechanistic study
Ramachandra, H
Rangappa, KS
Mahadevappa, DS
OXIDATION COMMUNICATIONS, 1997, 20 (04): : 565 - 575
[12] Kinetic and mechanistic studies on the oxidation of hydroxylamine, semicarbazide, and thiosemicarbazide by iron(III) in the presence of triazines
Susarla Ratnam
Nageswara Rao Anipindi
Transition Metal Chemistry, 2012, 37 : 453 - 462
[13] Ru(III)-Catalyzed L-Glutamic Acid Oxidation by Hexacyanoferrate(III) in an Anionic Surfactant Medium: A Kinetic and Mechanistic Approach
Srivastava, Abhishek
Singh, Ruchi
Srivastava, Neetu
Srivastava, Krishna
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A, 2023, 97 (07) : 1407 - 1415
[14] Kinetic and mechanistic studies on the oxidation of pyrrolidine by bis(hydrogenperiodato)argentate(III) complex anion
Jiong Zhang
Shuying Huo
Hongmei Shi
Shigang Shen
Yanli Shang
Transition Metal Chemistry, 2013, 38 : 15 - 20
[15] Kinetic and mechanistic studies on the oxidation of pyrrolidine by bis(hydrogenperiodato)argentate(III) complex anion
Zhang, Jiong
Huo, Shuying
Shi, Hongmei
Shen, Shigang
Shang, Yanli
TRANSITION METAL CHEMISTRY, 2013, 38 (01) : 15 - 20
[16] Ru(III)-Catalyzed L-Glutamic Acid Oxidation by Hexacyanoferrate(III) in an Anionic Surfactant Medium: A Kinetic and Mechanistic Approach
Abhishek Srivastava
Ruchi Singh
Neetu Srivastava
Krishna Srivastava
Russian Journal of Physical Chemistry A, 2023, 97 : 1407 - 1415
[17] Kinetic and mechanistic studies on the oxidation of hydroxylamine, semicarbazide, and thiosemicarbazide by iron(III) in the presence of triazines
Ratnam, Susarla
Anipindi, Nageswara Rao
TRANSITION METAL CHEMISTRY, 2012, 37 (05) : 453 - 462
[18] Mechanistic studies on the Ru(III)-catalyzed oxidation of some aromatic primary diamines by chloramine-T in hydrochloric acid medium: A kinetic approach
Shivananda, K. N.
Lakshmi, B.
Jagadeesh, R. V.
Puttaswamy
Mahendra, K. N.
APPLIED CATALYSIS A-GENERAL, 2007, 326 (02) : 202 - 212
[19] RU(III) CATALYSIS IN N-BROMOACETAMIDE OXIDATION OF ETHYLENE-GLYCOL AND GLYCEROL - A KINETIC AND MECHANISTIC STUDY
SINGH, B
SINGH, D
SINGH, AK
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1988, 20 (07) : 501 - 511
[20] Photocatalytic oxidation of cyanide: kinetic and mechanistic studies
Chiang, K
Amal, R
Tran, T
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2003, 193 (1-2) : 285 - 297

← 1 2 3 4 5 →