New iso and heteropolyoxomolybdates:: synthesis and molecular structure of the anions [Mo8VIO26(OH)]5-, [HAsIIIAsVMoVMo8VIO34]6- and [HAsIIIAsVMoVMo8VIO34{Co(C5H5N)2(H2O)3}]4-

被引:24
作者
Fidalgo, EG [1 ]
Neels, A [1 ]
Stoeckli-Evans, H [1 ]
Süss-Fink, G [1 ]
机构
[1] Univ Neuchatel, Inst Chim, CH-2007 Neuchatel, Switzerland
关键词
isopolyoxomolybdates; heteropolyoxomolybdates; hydrothermal synthesis; cobalt complexes;
D O I
10.1016/S0277-5387(02)01067-7
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The hydrothermal reaction of Na2MoO4 with pyridine in water at pH 5 and 130 degreesC gives the octamolybdate anion [Mo-8(VI) O-26(OH)](5-) (1) which crystallises as the pyridinium salt; its molecular structure derives from that of the parent alpha-octamolybdate anion [Mo-8(VI) O-26](4-) by opening two molybdenum-oxygen bond and adding a hydroxo bridge. The same reaction in the presence of NaAsO2 yields the mixed-valence arsenatomolybdate [Has(III)As(V)Mo(V)Mo(8)(VI)O(34)](6-) (2) which is also isolated as the pyridinium salt. Anion 2 has a lacunary structure like an open basket, which derives from the famous alpha-Keggin structure by removing three edge-sharing MoO6 octahedra and by capping a trioxygen face of three remaning MoO6 octahedra with an AsH group. Reaction of 2 with Co2+ leads to the anion [(HAsAsMoMo8VI)-As-III-Mo-V-Mo-V O-34 {Co(C5H5N)(2)(H2O)(3)}](4-) (3) which crystallises as a double pyridinium salt together with anion 2. The structure of 3 derives from that of 2 by attaching a Co(C5H5N)(2)(H2O)(3) fragment to a terminal oxo ligand. Reaction of 2 with hydrogen peroxide produces the fully oxydised alpha-Keggin anion [(AsMo12O40)-Mo-V-O-VI](3-) (4) which was found to crystallise as the tetrabutylammonium salt surprisingly with three independent molecules in the unit cell, two of them showing a remarkable disorder. (C) 2002 Elsevier Science Ltd. All rights reserved.
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页码:1921 / 1928
页数:8
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