Li Chifeng, Jimbo Atsuhiro, Yamaguchi Kazuya, Suzuki Kosuke
Department of Applied Chemistry, School of Engineering, The University of Tokyo 7-3-1 Hongo, Bunkyo-ku Tokyo 113-8656 Japan
Precursory Research for Embryonic Science and Technology (PRESTO), Japan Science and Technology Agency (JST) 4-1-8 Honcho, Kawaguchi Saitama 332-0012 Japan.
Chem Sci. 2021 Jan 13;12(4):1240-1244. doi: 10.1039/d0sc06133f.
Although metal-containing polyoxomolybdates (molybdenum oxide clusters) exhibit outstanding catalytic properties, their precise synthetic method has not yet been developed. This is mainly because the very low stability of the multivacant lacunary polyoxomolybdates limited their use as synthetic precursors. Here, we present a "protecting group strategy" in polyoxometalate synthesis and successfully develop an efficient method for synthesising multinuclear metal-containing polyoxomolybdates using pyridine as a protecting group for unstable trivacant lacunary Keggin-type polyoxomolybdate [PMoO]. Specifically, tetranuclear cubane- and planar-type manganese clusters were selectively synthesised in the polyoxomolybdates using the present method. The importance of this work is that, in addition to being the first practical way of utilizing multivacant lacunary polyoxomolybdates as precursors, this new "protecting group strategy" will make it possible to produce polyoxometalates with unexplored structures and properties.
尽管含金属的多氧钼酸盐（氧化钼簇）表现出出色的催化性能，但其精确的合成方法尚未开发出来。这主要是因为多空位缺位多氧钼酸盐的稳定性极低，限制了它们作为合成前体的应用。在此，我们提出了一种多金属氧酸盐合成中的“保护基策略”，并成功开发了一种高效的方法，以吡啶作为不稳定的三空位缺位Keggin型多氧钼酸盐[PMoO]的保护基，合成多核含金属多氧钼酸盐。具体而言，使用本方法在多氧钼酸盐中选择性地合成了四核立方烷型和平面型锰簇。这项工作的重要性在于，除了是将多空位缺位多氧钼酸盐用作前体的首个实用方法外，这种新的“保护基策略”将有可能制备出具有未探索结构和性能的多金属氧酸盐。
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