科研之友
微信
新浪微博
Facebook
分享链接
摘要
A series of aryldiazenido polyoxomolybdates of the type (nBu(4)N)(2)[Mo5O13(OMe)(4)(NNAr){Na(MeOH)}] (Ar = C6F5, 1; Ar = O2N-o-C6H4, 2; Ar = O2N-m-C6H4, 3; Ar = O2N-p-C6H4, 4a; Ar = (O2N)(2)-o,p-C6H3, 5) have been obtained by controlled degradation of the parent compounds (nBu(4)N)(3)[Mo6O18(NNAr)] with NaOH in methanol. They have been characterized by elemental analysis and UV-Vis and IR spectroscopy. In addition, 4a has been characterized by Mo-95 NMR spectroscopy and the crystal structure of (nBu(4)N)(2) [Mo5O13(OMe)(4)(NNC6H4-p-NO2){Na(H2O))]center dot H2O (4b) has been determined by X-ray diffraction. The molecular structure of the anion of 4b features a lacunary Lindqvist-type anion [Mo5O13(OMe)(4)(NNC6H4-p-NO2)](3) interacting with a sodium cation through the four terminal axial oxygen atoms. The 1:1 sodium complexes react with BaCl2 and BiCl3 to yield 2:1 complexes which have been isolated as (nBu(4)N)(4)[Ba{Mo5O13(OMe)(4)(NNAr)}(2)] (Ar = C6F5, 6; Ar = O2N-p-C6H4, 7) and (nBu(4)N)(3)[Bi{Mo5O13(OMe)(4)(NNAr)}(2)] (Ar = C6F5, 8; Ar = O2N-p-C6H4, 9). X-ray crystallography analysis of 9 center dot Me2CO has shown that the tetradentate [Mo5O13(OMe)(4)(N2C6H4-p-NO2)](3) anions provide a square-antiprismatic environment for Bi. In contrast, IR spectroscopy provides evidence for a square-prismatic environment of Ba in 6 and 7. In acetonitrile-methanol mixed solvent, [Mo5O13(OMe)(4)(NNAr)](3) and [PW11O39](7) , generated in situ by alkaline degradation of their respective parents, [Mo6O18(NNAr)](3) and [PW12O40](3) , react together to give the Keggin-type diazenido compounds (nBu(4)N)(4)[PW11O39(MoNNAr)] (Ar = O2N-o-C6H4, 10; Ar = O2N-m-C6H4, 11; Ar = O2N-p-C6H4, 12), which have been characterized by P-31 and W-183 NMR spectroscopy.
- 出版日期2010-12-10
