Cluster Oxalate Complexes [W3(μ3-Q)(μ2-Q)3 (C2O4)3(H2O)3]2− (Q=S, Se): Mechanochemical Synthesis and Crystal Structure.

Autor: Maxim Sokolov, Artyom Gushchin, Dmitrii Naumov, Olga Gerasko, Vladimir Fedin
Zdroj: Journal of Cluster Science; Sep2005, Vol. 16 Issue 3, p309-318, 10p
Abstrakt: Mechanochemical reaction of cluster coordination polymers $$^1_{\infty}[\hbox{W}_3\hbox{Q}_7\hbox{Br}_4]$$ (Q=S, Se) with solid $$\hbox{K}_2\hbox{C}_2\hbox{O}_4$$ leads to the cluster core excision with the formation of anionic complexes $$[\hbox{W}_3\hbox{Q}_7(\hbox{C}_2\hbox{O}_4)_3]^{2-}$$. Extraction of the reaction mixture with water followed by crystallization gives crystalline $$\hbox{K}_2[\hbox{W}_3\hbox{S}_7(\hbox{C}_2\hbox{O}_4)_3]\cdot 0.5 \hbox{KBr}\cdot 5\hbox{H}_2\hbox{O}$$ (main product) and $$\hbox{K}_2[\hbox{W}_3(\upmu_3 \hbox{-S})(\upmu_2 \hbox{-S})_3 (\hbox{H}_2\hbox{O})_3(\hbox{C}_2\hbox{O}_4)_3]\cdot 0.5\hbox{H}_2\hbox{C}_2\hbox{O}_4 \cdot 3\hbox{H}_2\hbox{O}$$ (1) (minor product). In the case of the Se cluster, the $$\hbox{W}_3\hbox{Se}_7$$ complex could not be isolated, and the treatment of the aqueous extract with PPh3 gave $$\hbox{K}_2[\hbox{W}_3(\upmu_{3}\hbox{-Se})(\upmu_2\hbox{-Se})_3 (\hbox{H}_2\hbox{O})_3(\hbox{C}_2\hbox{O}_4)_3]\cdot \hbox{H}_2\hbox{O}$$ (2) in a low yield. Alternatively, it was obtained from $$[\hbox{W}_3\hbox{Se}_4(\hbox{H}_2\hbox{O})_9]^{4+}$$ and $$\hbox{K}_2\hbox{C}_2\hbox{O}_4$$ in high yield. Both 1 and 2 were characterized by X-ray structure analysis. [ABSTRACT FROM AUTHOR]
Databáze: Complementary Index
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