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Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations : [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir). / Martynova, S. A.; Plyusnin, P. E.; Asanova, T. I. et al.

In: New Journal of Chemistry, Vol. 42, No. 3, 07.02.2018, p. 1762-1770.

Research output: Contribution to journal › Article › peer-review

Harvard

Martynova, SA, Plyusnin, PE, Asanova, TI, Asanov, IP, Pishchur, DP, Korenev, SV, Kosheev, SV, Floquet, S, Cadot, E & Yusenko, KV 2018, 'Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations: [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir)', New Journal of Chemistry, vol. 42, no. 3, pp. 1762-1770. https://doi.org/10.1039/c7nj04035k

APA

Martynova, S. A., Plyusnin, P. E., Asanova, T. I., Asanov, I. P., Pishchur, D. P., Korenev, S. V., Kosheev, S. V., Floquet, S., Cadot, E., & Yusenko, K. V. (2018). Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations: [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir). New Journal of Chemistry, 42(3), 1762-1770. https://doi.org/10.1039/c7nj04035k

Vancouver

Martynova SA, Plyusnin PE, Asanova TI, Asanov IP, Pishchur DP, Korenev SV et al. Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations: [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir). New Journal of Chemistry. 2018 Feb 7;42(3):1762-1770. doi: 10.1039/c7nj04035k

Author

Martynova, S. A. ; Plyusnin, P. E. ; Asanova, T. I. et al. / Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations : [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir). In: New Journal of Chemistry. 2018 ; Vol. 42, No. 3. pp. 1762-1770.

BibTeX

@article{52e117ae43c547079e5ae0dfdaa30c72,
title = "Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations: [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir)",
abstract = "[M(NH3)5Cl][IrCl6], M = Co, Cr, Ru, Rh, and Ir, were proposed as single-source precursors for bimetallic alloys. Their thermal decomposition in inert and reductive atmospheres below 700 °C results in the formation of nanostructured porous Ir0.5M0.5 alloys. Salts decompose with a significant exothermal effect during the first stage of their thermal breakdown in an inert atmosphere above 200 °C. The exothermal effect gradually decreases in the series: [Co(NH3)5Cl][IrCl6] (1) > [Cr(NH3)5Cl][IrCl6] (2) > [Ru(NH3)5Cl][IrCl6] (3) > [Rh(NH3)5Cl][IrCl6] (4); [Ir(NH3)5Cl][IrCl6] (5) does not exhibit any thermal effects and decomposes at much higher temperatures. To shed light on their thermal decomposition and the nature of the exothermal effect, DSC-EGA, in situ and ex situ IR, Raman, XPS and XAFS studies were performed. A combination of complementary techniques suggests a simultaneous ligand exchange and a reduction of central atoms as key processes. In [Co(NH3)5Cl][IrCl6], Co(iii) and Ir(iv) simultaneously oxidise coordinated ammonia, which can be detected due to a significant exothermal effect and the presence of Co(ii) and Ir(iii) in the intermediate product. The appearance of Ir-N frequencies demonstrates a ligand exchange between cations and the [IrCl6]2- anion. Salts with Cr(iii), Ru(iii), and Rh(iii) show a much lower exothermal effect due to the stability of their oxidation states. Salts with Rh(iii) and Ir(iii) demonstrate a high thermal stability and a low tendency for ligand exchange as well as decomposition with exothermal effects.",
keywords = "X-RAY-DIFFRACTION, CRYSTAL-STRUCTURE, OXIDATION-STATE, THERMOLYSIS, COMPLEXES, PLATINUM, PRODUCTS, IFEFFIT, XANES, RE",
author = "Martynova, {S. A.} and Plyusnin, {P. E.} and Asanova, {T. I.} and Asanov, {I. P.} and Pishchur, {D. P.} and Korenev, {S. V.} and Kosheev, {S. V.} and S. Floquet and E. Cadot and Yusenko, {K. V.}",
year = "2018",
month = feb,
day = "7",
doi = "10.1039/c7nj04035k",
language = "English",
volume = "42",
pages = "1762--1770",
journal = "New Journal of Chemistry",
issn = "1144-0546",
publisher = "ROYAL SOC CHEMISTRY",
number = "3",

}

RIS

TY - JOUR

T1 - Exothermal effects in the thermal decomposition of [IrCl6]2--containing salts with [M(NH3)5Cl]2+ cations

T2 - [M(NH3)5Cl][IrCl6] (M = Co, Cr, Ru, Rh, Ir)

AU - Martynova, S. A.

AU - Plyusnin, P. E.

AU - Asanova, T. I.

AU - Asanov, I. P.

AU - Pishchur, D. P.

AU - Korenev, S. V.

AU - Kosheev, S. V.

AU - Floquet, S.

AU - Cadot, E.

AU - Yusenko, K. V.

PY - 2018/2/7

Y1 - 2018/2/7

N2 - [M(NH3)5Cl][IrCl6], M = Co, Cr, Ru, Rh, and Ir, were proposed as single-source precursors for bimetallic alloys. Their thermal decomposition in inert and reductive atmospheres below 700 °C results in the formation of nanostructured porous Ir0.5M0.5 alloys. Salts decompose with a significant exothermal effect during the first stage of their thermal breakdown in an inert atmosphere above 200 °C. The exothermal effect gradually decreases in the series: [Co(NH3)5Cl][IrCl6] (1) > [Cr(NH3)5Cl][IrCl6] (2) > [Ru(NH3)5Cl][IrCl6] (3) > [Rh(NH3)5Cl][IrCl6] (4); [Ir(NH3)5Cl][IrCl6] (5) does not exhibit any thermal effects and decomposes at much higher temperatures. To shed light on their thermal decomposition and the nature of the exothermal effect, DSC-EGA, in situ and ex situ IR, Raman, XPS and XAFS studies were performed. A combination of complementary techniques suggests a simultaneous ligand exchange and a reduction of central atoms as key processes. In [Co(NH3)5Cl][IrCl6], Co(iii) and Ir(iv) simultaneously oxidise coordinated ammonia, which can be detected due to a significant exothermal effect and the presence of Co(ii) and Ir(iii) in the intermediate product. The appearance of Ir-N frequencies demonstrates a ligand exchange between cations and the [IrCl6]2- anion. Salts with Cr(iii), Ru(iii), and Rh(iii) show a much lower exothermal effect due to the stability of their oxidation states. Salts with Rh(iii) and Ir(iii) demonstrate a high thermal stability and a low tendency for ligand exchange as well as decomposition with exothermal effects.

AB - [M(NH3)5Cl][IrCl6], M = Co, Cr, Ru, Rh, and Ir, were proposed as single-source precursors for bimetallic alloys. Their thermal decomposition in inert and reductive atmospheres below 700 °C results in the formation of nanostructured porous Ir0.5M0.5 alloys. Salts decompose with a significant exothermal effect during the first stage of their thermal breakdown in an inert atmosphere above 200 °C. The exothermal effect gradually decreases in the series: [Co(NH3)5Cl][IrCl6] (1) > [Cr(NH3)5Cl][IrCl6] (2) > [Ru(NH3)5Cl][IrCl6] (3) > [Rh(NH3)5Cl][IrCl6] (4); [Ir(NH3)5Cl][IrCl6] (5) does not exhibit any thermal effects and decomposes at much higher temperatures. To shed light on their thermal decomposition and the nature of the exothermal effect, DSC-EGA, in situ and ex situ IR, Raman, XPS and XAFS studies were performed. A combination of complementary techniques suggests a simultaneous ligand exchange and a reduction of central atoms as key processes. In [Co(NH3)5Cl][IrCl6], Co(iii) and Ir(iv) simultaneously oxidise coordinated ammonia, which can be detected due to a significant exothermal effect and the presence of Co(ii) and Ir(iii) in the intermediate product. The appearance of Ir-N frequencies demonstrates a ligand exchange between cations and the [IrCl6]2- anion. Salts with Cr(iii), Ru(iii), and Rh(iii) show a much lower exothermal effect due to the stability of their oxidation states. Salts with Rh(iii) and Ir(iii) demonstrate a high thermal stability and a low tendency for ligand exchange as well as decomposition with exothermal effects.

KW - X-RAY-DIFFRACTION

KW - CRYSTAL-STRUCTURE

KW - OXIDATION-STATE

KW - THERMOLYSIS

KW - COMPLEXES

KW - PLATINUM

KW - PRODUCTS

KW - IFEFFIT

KW - XANES

KW - RE

UR - http://www.scopus.com/inward/record.url?scp=85041330502&partnerID=8YFLogxK

U2 - 10.1039/c7nj04035k

DO - 10.1039/c7nj04035k

M3 - Article

AN - SCOPUS:85041330502

VL - 42

SP - 1762

EP - 1770

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 3

ER -

ID: 12101889