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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) Full article

Journal New Journal of Chemistry
ISSN: 1144-0546 , E-ISSN: 1369-9261
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
Authors Martynova S.A. 1,2 , Plyusnin P.E. 1,2 , Asanova T.I. 1 , Asanov I.P. 1 , Pishchur D.P. 1 , Korenev S.V. 1,2 , Kosheev S.V. 3 , Floquet S. 4 , Cadot E. 4 , Yusenko K.V. 5,6
Affiliations
1 Nikolaev Institute of Inorganic Chemistry, Lavrentiev ave. 3, 630090 Novosibirsk, Russia
2 Novosibirsk State University, Pirogova str. 2, 630090 Novosibirsk, Russia
3 Novosibirsk, Boreskov Institute of Catalysis, 630090 Novosibirsk, Russia
4 Université de Versailles Saint-Quentin, Institut Lavoisier de Versailles (ILV), France
5 College of Engineering, Swansea University, Fabian Way, Swansea SA1 8EN, Wales, UK
6 Institute of Solid State Chemistry, Pervomaiskaia Str. 91, 620090 Ekaterinburg, Russia

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
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
Citing:
DB Citing
Web of science 13
Scopus 13
Elibrary 14
OpenAlex 14
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