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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Non-aqueous synthetic methodology for TiW5 polyoxometalates: protonolysis of [(MeO) TiW5O18](3-) with alcohols, water and phenols
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Non-aqueous synthetic methodology for TiW5 polyoxometalates: protonolysis of [(MeO) TiW5O18](3-) with alcohols, water and phenols

机译：TiW5多金属氧酸盐的非水合成方法：[（MeO）TiW5O18]（3-）与醇，水和酚的质子分解

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摘要

The tetra-n-butylammonium (TBA) salt of [(MeO)TiW5O18](3-) 1 was reacted with alcohols ROH to give primary, secondary and tertiary alkoxide derivatives [(RO)TiW5O18](3-) (R = Et 2, Pr-i 3 and Bu-t 4), whilst hydrolysis afforded [(mu-O)(TiW5O18)(2)](6-) 5 rather than the hydroxo derivative (R = H). In reactions with (PrOH)-Pr-i and (BuOH)-Bu-t, impurity peaks observed at 1015 and 1020 ppm in the O-17 NMR spectra indicate alkoxide degradation and Ti=O bond formation via reactions analogous to those occurring at the surfaces of solid heteropolyacids. Aryloxides [(ArO)TiW5O18](3-) were prepared by reacting 1 with phenols ArOH ( Ar = C6H5 6, C6H4Me-4 7, (C6H4Bu)-Bu-t-4 8, C6H4OH-4 9, C6H4OH-3 10, C6H3(OH)(2)- 3,5 11 and C6H4CHO-2 13). TiW5O18 units were linked by reacting 1 with 9 to give [(mu-1,4-OC6H4O)-(TiW5O18)(2)](6-) 12. O-17 and W-183 NMR spectra are reported and X-ray crystal structures were obtained for TBA salts of anions 3-10 and 13, which showed that the titanium is six-coordinate in all cases. Reactions were monitored by H-1 NMR, including a 2D-EXSY study of methoxo exchange, and the slow rates observed are probably associated with the reluctance of titanium in these anions to achieve seven-coordination.
机译：使[（MeO）TiW5O18]（3-）1的四正丁基铵（TBA）盐与醇ROH反应，生成伯，仲和叔醇盐衍生物[（RO）TiW5O18]（3-）（R = Et 2，Pr-i 3和Bu-t 4），同时水解得到[（mu-O）（TiW5O18）（2）]（6-）5而不是羟基衍生物（R = H）。在与（PrOH）-Pr-i和（BuOH）-Bu-t的反应中，O-17 NMR光谱中的1015和1020 ppm处观察到的杂质峰表明醇盐的降解和Ti = O键的形成与反应类似固体杂多酸的表面。通过使1与酚ArOH反应制备芳氧基化合物[（ArO）TiW5O18]（3-）（Ar = C6H5 6，C6H4Me-4 7，（C6H4Bu）-Bu-t-4 8，C6H4OH-4 9，C6H4OH-3 10 ，C6H3（OH）（2）-3,5 11和C6H4CHO-2 13）。通过使1与9反应连接TiW5O18单元，得到[（mu-1,4-OC6H4O）-（TiW5O18）（2）]（6-）12。报道了O-17和W-183 NMR光谱，并进行了X射线分析获得了阴离子3-10和13的TBA盐的晶体结构，表明钛在所有情况下均为六配位。反应通过H-1 NMR进行监测，包括2D-EXSY研究方法的甲氧羰基交换，观察到的缓慢速率可能与这些阴离子中钛缺乏实现七配位的意愿有关。

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