4:2钼、钨过氧配合物的制备、结构及其氧化还原分解行为

本文作者曾在用过钨酸分解法制备钨酸的过程中发现, 溶液中W与O2^2^-之比始终为2:1, 这一事实说明溶液中有2:1金属过氧配合物形成, 2:1铂过氧络合物Mo4O12(O2)2]^4^-文献上已有记载, 但类似的钨配合物尚未见报道。本文制备了这二种配合物, 对比它们的红外和Raman光谱, 并用循环伏安法, 恒电位电解法探讨它们的氧化还原分解体系。

Preparation, structure and behaviour of peroxymolybdate [K4Mo4O12(O2)2] and peroxytungstate [K4W4O12(O2)2.4H2O]

K4Mo4O12(O2)2 and K4W4O12(O2)2.4H2O were prepared from K2MoO4 or K2WO4, resp., and H2O2 at pH 7.3. The products were characterized by IR, Raman and cyclic voltammetry studies. Both compounds were reduced at a Pt electrode vs. SCE at E1 = 0.317, 0.172 V, resp. and E2 = 0.226, <-0.2 V, resp. They were oxidized at E3 = 0.862, 0.786 V, resp. The Mo compound decomposed after a 1-electron reduction Both compounds decomposed after the 4-electron oxidation at E3.