REACTION OF transꢀ[RuNO(NH3)4(OH)]Cl2
1153
6. M. A. Il’in, E. V. Kabin, V. A. Emel’yanov, et al.,
When the complex is refluxed in 8 M HNO3, reacꢀ
tions (1)–(5) occur in the system, and a mixture of
J. Struct. Chem. 50, 328 (2009).
complexes I and II is deposited.
7. N. M. Sinitsyn and V. V. Borisov, Zh. Neorg. Khim. 19
,
1688 (1974).
An increase in the nitric acid concentration leads
to partial destruction of the tetraammine complex by
reaction (6)–(10), and the reaction products are mixꢀ
tures of poorly soluble complexes II and III. The oxiꢀ
dation of ammonia molecules is preceded by their
passing into the solution volume at high acidity and
+
8. M. N. Sinitsyn and A. A. Svetlov, Zh. Neorg. Khim. 25
,
3063 (1980).
9. A. S. Kanishcheva, Yu. N. Mikhailov, and A. A. Svetlov,
Zh. Neorg. Khim. 35, 1760 (1990).
10. V. A. Emel’yanov, E. V. Kabin, and I. A. Baidina,
J. Struct. Chem. 50, 577 (2009).
temperature ((6), (9)). The resulting
oxidized by reaction (7).
cation is
NH4
11. E. V. Kabin, V. A. Emel’yanov, I. A. Baidina, et al.,
J. Struct. Chem. 51, S73 (2010).
The use of concentrated nitric acid makes it possible
to separate the reactions of formation of complexes II
and III in time and isolate them as individual comꢀ
pounds. The insufficiently high yield of complex III is
caused by the occurrence of reaction (1).
12. V. A. Emel’yanov, S. P. Khranenko, and A. V. Belyaev,
Russ. J. Inorg. Chem. 46, 346 (2001).
13. M. A. Il’in, V. A. Emel’yanov, A. V. Belyaev, et al., Russ.
J. Inorg. Chem. 53, 1070 (2008).
14. E. E. Mercer, W. A. McAlister, and J. R. Durig, Inorg.
Attempts to stop the process at the stage of formaꢀ
tion of triamminenitrosoruthenium complexes (reacꢀ
Chem. 5, 1881 (1966).
tions (6) and (8)) by varying the HNO3 concentration 15. The International Centre for Diffraction Data Powder
Diffraction File 2001 (ICDD/JCPDS PDF 2001).
and heating duration were unsuccessful. In these runs,
the products are mixtures of complexes II and III. The
treatment of mother liquors with hydrochloric acid on
heating also leads to mixtures of tetraꢀ and diammineniꢀ
16. K. Nakamoto, Infrared Spectra of Inorganic and Coorꢀ
dination Compounds (Wiley, New York, 1963; Mir, Mosꢀ
cow, 1966).
trosoruthenium complexes transꢀ[RuNO(NH3)4Cl]Cl2
17. NutsPro 6.0, NMR Utility Transform Software, 2D
Professional Version 20060331, Acorn NMR, 1993–
2005.
and facꢀ[RuNO(NH3)2Cl3]. This is most likely caused
by the fact that the rate of reaction (9) is considerably
higher than the rate of reaction (6).
18. G. M. Sheldrick, SHELXꢀ97, Release 97ꢀ1, Univ. of
Göttingen, Göttingen, Germany, 1997.
19. V. A. Emel’yanov, A. V. Virovets, I. A. Baidina, et al.,
ACKNOWLEDGMENTS
Inorg. Chem. Commun. 4, 33 (2001).
This work was supported by the Division of Chemistry
and Materials Science of the RAS (project no. 5.9) and
the Federal Targeted Program “Scientific and Scienꢀ
tificꢀPedagogical Personnel of the Innovative Russia
in 2009–2013” (State contract nos. 02.740.11.0628
and P280 of 23.07.09).
20. N. M. Sinitsyn, V. N. Kokunova, G. G. Novitskii, et al.,
Zh. Neorg. Khim. 33, 2056 (1988).
21. M. N. Sinitsyn, A. A. Svetlov, A. S. Kanishcheva, et al.,
Zh. Neorg. Khim. 34, 2795 (1989).
22. A. A. Svetlov, N. M. Sinitsyn, and V. V. Kravchenko,
Zh. Neorg. Khim. 34, 2571 (1989).
23. 3. M. A. Fedotov and A. V. Belyaev, Koord. Khim. 17
,
103 (1991).
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RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 57 No. 8 2012