Selective Two-Step Oxidation of μ2-S Ligands in Trigonal Prismatic Unit {Re3(μ6-C)(μ2-S)3Re3} of the Bioctahedral Cluster Anion [Re12CS17(CN)6]6–

Selective Two-Step Oxidation of μ2-S Ligands in Trigonal Prismatic Unit {Re3(μ6-C)(μ2-S)3Re3} of the Bioctahedral Cluster Anion [Re12CS17(CN)6]6– Full article

Journal

Inorganic Chemistry
ISSN: 0020-1669 , E-ISSN: 1520-510X

Output data

Year: 2012, Volume: 51, Number: 7, Pages: 4359-4367 Pages count : 8 DOI: 10.1021/ic300051w

Tags

Anions, Cluster chemistry, Cluster structure, Ligands, Oxidation

Authors

Mironov Yuri V. ¹ , Gayfulin Yakov M. ¹ , Kozlova Svetlana G. ¹ , Smolentsev Anton I. ¹ , Tarasenko Maria S. ¹ , Nizovtsev Anton S. ¹ , Fedorov Vladimir E. ¹

Affiliations

1	Nikolaev Institute of Inorganic Chemistry, Siberian Branch of the Russian Academy of Sciences, 3 Acad. Lavrentiev Prospect, 630090 Novosibirsk, Russia

An oxidation of cluster anion [Re12CS17(CN)6]6– by H2O2 in water has been investigated. It was shown that selective two-step oxidation of bridging μ2-S-ligands in trigonal prismatic unit {Re3(μ6-C)(μ2-S)3Re3} takes place. The first stage runs rapidly, whereas the speed of the second stage depends on intensity of ultraviolet irradiation of the reaction mixture. Each stage of the reaction is accompanied by a change in the solution’s color. In the first stage of the oxidation, the cluster anion [Re12CS14(SO2)3(CN)6]6– is produced, in which all bridging S-ligands are turned into bridging SO2-ligands. The second stage of the oxidation leads to formation of the anion [Re12CS14(SO2)2(SO3)(CN)6]6–, in which one of the SO2-ligands underwent further oxidation forming the bridging SO3-ligand. Seven compounds containing these anions were synthesized and characterized by a set of different methods, elemental analyses, IR and UV/vis spectroscopy, and quantum-chemical calculations. Structures of some compounds based on similar cluster anions, [Cu(NH3)5]3[Re12CS14(SO2)3(CN)6]·9.5H2O, [Ni(NH3)6]3[Re12CS14(SO2)3(CN)6]·4H2O, and [Cu(NH3)5]2.6[Re12CS14(SO2)3(CN)6]0.6[{Re12CS14(SO2)2(SO3)(CN)5(μ-CN)}{Cu(NH3)4}]0.4·5H2O, were investigated by X-ray analysis of single crystals.

Mironov Y.V. , Gayfulin Y.M. , Kozlova S.G. , Smolentsev A.I. , Tarasenko M.S. , Nizovtsev A.S. , Fedorov V.E.
Selective Two-Step Oxidation of μ2-S Ligands in Trigonal Prismatic Unit {Re3(μ6-C)(μ2-S)3Re3} of the Bioctahedral Cluster Anion [Re12CS17(CN)6]6–
Inorganic Chemistry. 2012. V.51. N7. P.4359-4367. DOI: 10.1021/ic300051w WOS Scopus OpenAlex

Submitted:	Jan 12, 2012
Accepted:	Jan 12, 2012
Published print:	Mar 12, 2012
Published online:	Mar 12, 2012

Web of science:	WOS:000302186600057
Scopus:	2-s2.0-84859220982
OpenAlex:	W2150900000

DB	Citing
OpenAlex	22
Scopus	23
Web of science	20