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) | Sciact - CRIS-system of Boreskov Institute of Catalysis

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)

Russian Science Foundation

16-13-10192

[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.

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

Full text from publisher

Submitted:	Oct 18, 2017
Accepted:	Dec 12, 2017
Published online:	Dec 12, 2017
Published print:	Feb 7, 2018

Web of science:	WOS:000423702900028
Scopus:	2-s2.0-85041330502
Elibrary:	35520470
Chemical Abstracts:	2017:1954390
Chemical Abstracts (print):	168:174504
OpenAlex:	W2773516309

DB	Citing
Web of science	13
Scopus	13
Elibrary	15
OpenAlex	14