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) Full article
Journal |
New Journal of Chemistry
ISSN: 1144-0546 , E-ISSN: 1369-9261 |
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Output data | Year: 2018, Volume: 42, Number: 3, Pages: 1762-1770 Pages count : 9 DOI: 10.1039/c7nj04035k | ||||||||||||
Tags | X-RAY-DIFFRACTION; CRYSTAL-STRUCTURE; OXIDATION-STATE; THERMOLYSIS; COMPLEXES; PLATINUM; PRODUCTS; IFEFFIT; XANES; RE | ||||||||||||
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Affiliations |
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Funding (1)
1 | Russian Science Foundation | 16-13-10192 |
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.
Cite:
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.
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. V.42. N3. P.1762-1770. DOI: 10.1039/c7nj04035k WOS Scopus РИНЦ ANCAN OpenAlex
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. V.42. N3. P.1762-1770. DOI: 10.1039/c7nj04035k WOS Scopus РИНЦ ANCAN OpenAlex
Files:
Full text from publisher
Dates:
Submitted: | Oct 18, 2017 |
Accepted: | Dec 12, 2017 |
Published online: | Dec 12, 2017 |
Published print: | Feb 7, 2018 |
Identifiers:
Web of science: | WOS:000423702900028 |
Scopus: | 2-s2.0-85041330502 |
Elibrary: | 35520470 |
Chemical Abstracts: | 2017:1954390 |
Chemical Abstracts (print): | 168:174504 |
OpenAlex: | W2773516309 |