School of Chemistry, Trinity College, The University of Dublin, Dublin 2, Ireland.
Inorg Chem. 2011 Jan 17;50(2):604-13. doi: 10.1021/ic101672t. Epub 2010 Dec 8.
We report here a facile synthetic and analytical approach that allows us to identify and characterize functionalized polyoxomolybdate clusters that form upon the partial reduction of Mo(VI) salts in the presence of organoarsonate ligands. We demonstrated that electrospray ionization mass spectrometry, in combination with X-ray crystallography, provides an extremely powerful tool, allowing us to exploit slight perturbations of the ligand structures for the preparation of a series of unprecedented cluster compounds. Redox-active transition metals that adopt cubane or related structures are of particular interest because of their resemblance to active sites of enzymes. Our investigations underline the stability of the hybrid compounds in solution, an essential requirement for potential applications as catalysts. Supplemental analyses include measurements of the magnetic properties, NMR, IR, UV/vis, and bond-valence-sum analyses. Our results highlight the possibility of exploring real-time growth reactions of polyoxometales that emerge in solution and transform to produce hybrid organic-inorganic polyoxometalate clusters.
我们在这里报告了一种简便的合成和分析方法，该方法可用于鉴定和表征在有机胂酸盐配体存在下部分还原 Mo(VI)盐时形成的功能化多钼酸盐簇。我们证明，电喷雾电离质谱法（ESI-MS）结合 X 射线晶体学为我们提供了一种极其强大的工具，使我们能够利用配体结构的微小变化来制备一系列前所未有的簇化合物。采用立方烷或相关结构的氧化还原活性过渡金属因其与酶的活性位点相似而受到特别关注。我们的研究强调了混合化合物在溶液中的稳定性，这是作为催化剂潜在应用的基本要求。补充分析包括磁性测量、NMR、IR、UV/vis 和键价和分析。我们的结果突出了探索在溶液中出现并转化为产生混合有机-无机多金属氧酸盐簇的多金属氧酸盐实时生长反应的可能性。
