Thakur Arunabha, Chakraborty Amarnath, Ramkumar V, Ghosh Sundargopal
Department of Chemistry, Indian Institute of Technology Madras, Chennai, 600 036, India.
Dalton Trans. 2009 Sep 28(36):7552-8. doi: 10.1039/b908348k. Epub 2009 Jul 27.
Two fully oxidized [(n-Bu4N)2][Mo6O19], 7 and [(n-Bu4N)2][W6O19], 8 and one mixed-metal, mixed-valence one electron reduced [(n-Bu4N)3][MoW5O19], 9 cluster have been synthesized under biphasic reaction conditions from group VI metal carbonyls or Fischer carbene complexes, [(CO)5M=C(OMe)Me] (M = Mo, W) in yields of 73, 77 and 71% respectively. All the clusters have been characterized by IR, 1H and 13C NMR spectra, and crystal structure determinations. Additionally, the composition of 9 has also been supported by mass spectrometry (MALDI-TOF), inductively coupled plasma (ICP) and energy-dispersive X-ray (EDX) analysis. This novel and mild route offers distinct improvements over earlier methods of synthesis for Lindqvist type mixed-valence mixed-metal polyoxometalate cluster.
在双相反应条件下，由VI族金属羰基化合物或费舍尔卡宾配合物[(CO)5M = C(OMe)Me]（M = Mo、W）合成了两种完全氧化的[(n-Bu4N)2][Mo6O19]（7）和[(n-Bu4N)2][W6O19]（8）以及一种混合金属、混合价态的单电子还原产物[(n-Bu4N)3][MoW5O19]（9）簇合物，产率分别为73%、77%和71%。所有簇合物均通过红外光谱、1H和13C核磁共振谱以及晶体结构测定进行了表征。此外，9的组成也得到了质谱（基质辅助激光解吸电离飞行时间质谱）、电感耦合等离子体（ICP）和能量色散X射线（EDX）分析的支持。与早期合成Lindqvist型混合价态混合金属多金属氧酸盐簇合物的方法相比，这条新颖且温和的路线有显著改进。
