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

Mechanochemical reaction of cluster coordination polymers \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$^1_{\infty}[\hbox{W}_3\hbox{Q}_7\hbox{Br}_4]$$\end{document} (Q=S, Se) with solid \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox{K}_2\hbox{C}_2\hbox{O}_4$$\end{document} leads to the cluster core excision with the formation of anionic complexes \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$[\hbox{W}_3\hbox{Q}_7(\hbox{C}_2\hbox{O}_4)_3]^{2-}$$\end{document}. Extraction of the reaction mixture with water followed by crystallization gives crystalline \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox{K}_2[\hbox{W}_3\hbox{S}_7(\hbox{C}_2\hbox{O}_4)_3]\cdot 0.5 \hbox{KBr}\cdot 5\hbox{H}_2\hbox{O}$$\end{document} (main product) and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox{K}_2[\hbox{W}_3(\upmu_3 \hbox{-S})(\upmu_2 \hbox{-S})_3 (\hbox{H}_2\hbox{O})_3(\hbox{C}_2\hbox{O}_4)_3]\cdot 0.5\hbox{H}_2\hbox{C}_2\hbox{O}_4 \cdot 3\hbox{H}_2\hbox{O}$$\end{document} (1) (minor product). In the case of the Se cluster, the \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox{W}_3\hbox{Se}_7$$\end{document} complex could not be isolated, and the treatment of the aqueous extract with PPh3 gave \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox{K}_2[\hbox{W}_3(\upmu_{3}\hbox{-Se})(\upmu_2\hbox{-Se})_3 (\hbox{H}_2\hbox{O})_3(\hbox{C}_2\hbox{O}_4)_3]\cdot \hbox{H}_2\hbox{O}$$\end{document} (2) in a low yield. Alternatively, it was obtained from \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$[\hbox{W}_3\hbox{Se}_4(\hbox{H}_2\hbox{O})_9]^{4+}$$\end{document} and \documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox{K}_2\hbox{C}_2\hbox{O}_4$$\end{document} in high yield. Both 1 and 2 were characterized by X-ray structure analysis.