Mapping the synthesis of low nuclearity polyoxometalates from octamolybdates to Mn-Anderson clusters.
Mapping the synthesis of low nuclearity polyoxometalates from octamolybdates to Mn-Anderson clusters.
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DOI：
10.1039/c2dt31008b
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发表时间：
2012-07
影响因子：
4
通讯作者：
Mali H. Rosnes;Carine Yvon;D. Long;L. Cronin
中科院分区：
文献类型：
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作者：
Mali H. Rosnes;Carine Yvon;D. Long;L. Cronin
本文报道了由Na(2)MoO(4)·2H(2)O通过相应的八钼酸盐物种合成三((HOCH(2))(3)CNH(2))Mn-Anderson化合物的非同分异构体的综合研究。以钼酸钠为起始原料，以四甲基铵、四乙基铵和四丙基铵为反阳离子，合成了三种β异构体的八钼盐[Mo(8)O(26)](4-)。通过元素分析、热重分析、溶液和固态拉曼光谱、红外光谱和电喷雾质谱等手段对产物进行了表征，结果表明三种化合物均含有一定比例的有机阳离子和钠离子；(TMA)(2)Na(2)[Mo(8)O(26)](1)，(TEA)(3)Na(1)[Mo(8)O(26)](2)和(TPA)(2)Na(2)[Mo(8)O(26)](3)，分析还证实这三个化合物都是以β-异构体形式存在的八钼酸盐。1、2和3的电喷雾质谱分析表明，与先前报道的合成((TBA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)])(B)中的β-异构体((Tba)(4)[α-Mo(8)O(26)])(A)的研究相比，这些α-异构体的裂解相似，以及化合物1，2和3被成功地用于合成等价的Tris Mn-Anderson化合物：(TMA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)](4)，(TEA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)](5)和(TPA)(2)Na(1)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)](6)以及Na(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)](7)。这是第一个在二甲基甲酰胺中用{Mo(8)O(26)}α异构体以外的任何物质合成对称有机接枝的锰-安德森化合物的例子。
A comprehensive study of the isomer-independent synthesis of TRIS ((HOCH(2))(3)CNH(2)) Mn-Anderson compounds from Na(2)MoO(4)·2H(2)O, via the corresponding octamolybdate species, is presented. Three octamolybdate salts of [Mo(8)O(26)](4-) in the β-isomer form, with tetramethylammonium (TMA), tetraethylammonium (TEA) and tetrapropylammonium (TPA) as the counter cation, were synthesised from the sodium molybdate starting material. Fine white powdery products for the three compounds were obtained, which were fully characterised by elemental analysis, TGA, solution and solid state Raman, IR and ESI-MS, revealing a set ratio of Na and organic cations for each of the three compounds; (TMA)(2)Na(2)[Mo(8)O(26)] (1), (TEA)(3)Na(1)[Mo(8)O(26)] (2) and (TPA)(2)Na(2)[Mo(8)O(26)] (3), and the analyses also confirmed that the three compounds all consisted of the octamolybdate in the β-isomeric form. ESI-MS analyses of 1, 2 and 3 show similar fragmentation for these β-isomers compared to the previously reported study for the α-isomer ((TBA)(4)[α-Mo(8)O(26)]) (A) in the synthesis of ((TBA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)]) (B), and compounds 1, 2 and 3 were successfully used to synthesise equivalent TRIS Mn-Anderson compounds: (TMA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (4), (TEA)(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (5) and (TPA)(2)Na(1)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (6), as well as Na(3)[MnMo(6)O(18)((OCH(2))(3)CNH(2))(2)] (7). This is the first example where symmetric organically-grafted Mn-Anderson compounds have been synthesised in DMF from anything but the {Mo(8)O(26)} α-isomer.