4 years ago

An Unprecedented Class of Benzoyldiazenido Functionalized Polyoxometalates with Enhanced Anti-tumour Activity

Yongge Wei, Jin Zhang, Wei-Wei Fu, Feng-Ping Xiao, Shi-jia Xue, Panchao Yin, Zhi-Kun Fang, Longsheng Wang
An unprecedented class of benzoyldiazenido functionalized polyoxometalates, (Bu4N)3[Mo6O18(=N=NCOAr)] (Ar = Ph, 1; Ph-o-Cl, 2; Ph-m-Cl, 3; Ph-p-Cl, 4; Ph-o, p-Cl2, 5; Ph-p-Br, 6; Ph-m-NO2, 7; Ph-p-NO2, 8; Ph-p-OMe, 9) are prepared via the refluxing reaction of α-octamolybdates and corresponding hydrazides in dry acetonitrile using dicyclohexylcarbodiimide (DCC) as dehydrating agent. Single crystal X-ray diffraction structural analysis reveals that their anions demonstrate typical structural features of mono-functionalized hexamolybdates with different organic substituents. 1H NMR indicates that the [Mo6O18(NN)] fragment in these compounds is an electron-donating group rather than an electron-withdrawing group, which is further validated by the calculation of atomic charge distribution(natural bond orbital (NBO) and Mülliken). Bond valence sum (BVS) shows that the oxidation state of all molybdenum atoms is +6. Cyclic voltammetry (CV) indicates that they are more difficult to be reduced than hexamolybdate and its organoimido derivatives. Anti-tumour activity test against K562 shows that most hybrid compounds have an enhanced inhibitory activity compared to hexamolybdate and corresponding hydrazide ligands.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/ejic.201700990

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