Formation and Conversion of Yellow Molybdophosphonate Complexes in Aqueous-Organic Media
作者:Tadaharu Ueda、Ken-ichi Sano、Sadayuki Himeno、Toshitaka Hori
DOI:10.1246/bcsj.70.1093
日期:1997.5
The reaction of Mo(VI) with PHO32− in acidic solution containing CH3COCH3 or CH3CN led to the formation of the previously unknown 15-molybdobis(phosphonate) complex. The addition of an excess of PHO32− caused 15-molybdobis(phosphonate) to transform into 16-molybdotetrakis(phosphonate) in the CH3COCH3–water system. In the CH3CN–water system, on the other hand, the spontaneous transformation of 15-molybdobis(phosphonate) into 12-molybdobis(phosphonate) occurred in the presence of an excess of PHO32− or at greater acidities; the latter complex was also formed in aqueous media. The yellow heteropolyanions underwent electrochemical reductions, yielding mixed-valence blue species.
Mo(VI) 与 PHO32− 在含有 CH3COCH3 或 CH3CN 的酸性溶液中反应,形成了以前未知的 15-钼双(膦酸盐)络合物。添加过量的 PHO32− 会导致 CH3COCH3-水体系中的 15-钼二(膦酸盐)转化为 16-钼四(膦酸盐)。另一方面,在 CH3CN-水体系中,当存在过量的 PHO32− 或酸度较高时,15-钼双(膦酸盐)会自发转化为 12-钼双(膦酸盐)。后一种复合物也在水介质中形成。黄色杂多阴离子经历电化学还原,产生混合价蓝色物质。