Sokolov, Maxim N. Gushchin, Artyom L. Naumov, Dmitrii Yu. Gerasko, Olga A. Fedin, Vladimir P. Cluster Oxalate Complexes [M<sub>3</sub>(μ<sub>3</sub>-Q)(μ<sub>2</sub>-Q<sub>2</sub>)<sub>3</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sup>2-</sup> and [Mo<sub>3</sub>(μ<sub>3</sub>-Q)(μ<sub>2</sub>-Q)<sub>3</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]<sup>2-</sup> (M = Mo, W; Q = S, Se):  Mechanochemical Synthesis and Crystal Structure Mechanochemical reaction of cluster coordination polymers <sup>1</sup><sub>∞</sub>[M<sub>3</sub>Q<sub>7</sub>Br<sub>4</sub>] (M = Mo, W; Q = S, Se) with solid K<sub>2</sub>C<sub>2</sub>O<sub>4</sub> leads to cluster core excision with the formation of anionic complexes [M<sub>3</sub>Q<sub>7</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sup>2-</sup>. Extraction of the reaction mixture with water followed by crystallization gives crystalline K<sub>2</sub>[M<sub>3</sub>Q<sub>7</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·0.5KBr·<i>n</i>H<sub>2</sub>O (M = Mo, Q = S, <i>n</i> = 3 (<b>1</b>); M = Mo, Q = Se, <i>n</i> = 4 (<b>2</b>); M = W, Q = S, <i>n</i> = 5 (<b>3</b>)). Cs<sub>2</sub>[Mo<sub>3</sub>S<sub>7</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]·0.5CsCl·3.5H<sub>2</sub>O (<b>4</b>) and (Et<sub>4</sub>N)<sub>1.5</sub>H<sub>0.5</sub>K{[Mo<sub>3</sub>S<sub>7</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]Br}·2H<sub>2</sub>O (<b>5</b>) were also prepared. Close Q···Br contacts result in the formation of ionic triples {[M<sub>3</sub>Q<sub>7</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]<sub>2</sub>Br}<sup>5-</sup> in <b>1</b><b>−</b><b>4</b> and the 1:1 adduct {[Mo<sub>3</sub>S<sub>7</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>]Br}<sup>3-</sup> in <b>5</b>. Treatment of <b>1</b> or <b>2</b> with PPh<sub>3</sub> leads to chalcogen abstraction with the formation of [Mo<sub>3</sub>(μ<sub>3</sub>-Q)(μ<sub>2</sub>-Q)<sub>3</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]<sup>2-</sup>, isolated as (Ph<sub>4</sub>P)<sub>2</sub>[Mo<sub>3</sub>(μ<sub>3</sub>-S)(μ<sub>2</sub>-S)<sub>3</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]·11H<sub>2</sub>O (<b>6</b>) and (Ph<sub>4</sub>P)<sub>2</sub>[Mo<sub>3</sub>(μ<sub>3</sub>-Se)(μ<sub>2</sub>-Se)<sub>3</sub>(C<sub>2</sub>O<sub>4</sub>)<sub>3</sub>(H<sub>2</sub>O)<sub>3</sub>]·8.5H<sub>2</sub>O·0.5C<sub>2</sub>H<sub>5</sub>OH (<b>7</b>). All compounds were characterized by X-ray structure analysis. IR, Raman, electronic, and <sup>77</sup>Se NMR spectra are also reported. Thermal decomposition of <b>1</b><b>−</b><b>3</b> was studied by thermogravimetry. PPh 3;77 Se NMR spectra;OH;reaction mixture;M 3 Q 7;Crystal Structure Mechanochemical reaction;chalcogen abstraction;C 2 O 4;M 3 Q 7 Br 4;Cluster Oxalate Complexes;Thermal decomposition;H 2 O;Q 2;2 Br;K 2;K 2 C 2 O 4;Et 4 N;cluster core excision;Mo 3 S 7;IR;Ph 4 P 2005-04-04
    https://acs.figshare.com/articles/dataset/Cluster_Oxalate_Complexes_M_sub_3_sub_sub_3_sub_Q_sub_2_sub_Q_sub_2_sub_sub_3_sub_C_sub_2_sub_O_sub_4_sub_sub_3_sub_sup_2_sup_and_Mo_sub_3_sub_sub_3_sub_Q_sub_2_sub_Q_sub_3_sub_C_sub_2_sub_O_sub_4_sub_sub_3_sub_H_sub_2_sub_O_sub_3_sub_sup_2_sup_M_Mo_W_Q_S/3292978
10.1021/ic0488637.s006