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首页> 外文期刊>Chemistry: A European journal >Oxygenation Chemistry of Magnesium Alkyls Incorporating beta-Diketiminate Ligands Revisited
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Oxygenation Chemistry of Magnesium Alkyls Incorporating beta-Diketiminate Ligands Revisited

机译：重新研究了掺入β-二甲叉基配体的镁烷基镁的氧合化学

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Despite the fact that extensive research has been carried out, the oxygenation of alkyl magnesium species still remains a highly unexplored research area and significant uncertainties concerning the mechanism of these reactions and the composition of the resulting products persist. This case study compares the viability of the controlled oxygenation of alkylmagnesium complexes supported by beta-diketiminates. The structural tracking of the reactivity of (N,N) MgR-type complexes towards O-2 at low temperature showed that their oxygenation led exclusively to the formation of magnesium alkylperoxides (N,N)MgOOR. The results also highlight significant differences in the stability of the resulting alkylperoxides in solution and demonstrate that [(BDI)Mg(mu-eta(2):eta(1)-OOBn)](2) (in which BDI=[(ArNCMe)(2)CH](-) and Ar=C(6)H(3)iPr(2)-2,6) can be easily transformed to the corresponding magnesium alkoxide [(BDI)MgOBn](2) at ambient temperature, whilst [((BDI)-B-F3)Mg(mu-OOtBu)](2) (in which (BDI)-B-F3=[(ArNCMe)(2)CH](-) and Ar=C6H2F3-2,4,6) is stable under similar conditions. The observed selective oxygenation of (N,N)MgR-type complexes to the corresponding (N,N)MgOOR alkylperoxides strongly contradicts the widely accepted radical-chain mechanism for the oxygenation of the main-group-metal alkyls. Furthermore, either the observed transformation of the alkylperoxide [(BDI)MgOOBn](2) to the alkoxide [(BDI)MgOBn](2) as well as the formation of an intractable mixture of products in the control reaction between the alkylperoxide [((BDI)-B-F3)MgOOtBu](2) and the parent alkylmagnesium [((BDI)-B-F3)MgtBu] complex are not in line with the common wisdom that magnesium alkoxide complexes' formation results from the metathesis reaction between MgOOR and Mg-R species. In addition, a high catalytic activity of well-defined magnesium alkylperoxides, in combination with tert-butyl hydroperoxide (TBHP) as an oxygen source, in the epoxidation of trans-chalcone is presented.
机译：尽管已经进行了广泛的研究，但是烷基镁物质的氧合仍然是一个尚未高度研究的领域，并且关于这些反应的机理和所得产物的组成仍然存在很大的不确定性。本案例研究比较了β-二酮化合物支持的烷基镁配合物受控氧合的可行性。 （N，N）MgR型配合物在低温下对O-2的反应活性的结构追踪表明，它们的氧合仅导致烷基过氧化镁（N，N）MgOOR的形成。结果还突出显示了所得烷基过氧化物在溶液中的稳定性方面的显着差异，并证明了[（BDI）Mg（mu-eta（2）：eta（1）-OOBn）]（2）（其中BDI = [（ArNCMe ）（2）CH]（-）和Ar = C（6）H（3）iPr（2）-2,6）在环境温度下可以轻松转化为相应的烷氧基镁[（BDI）MgOBn]（2） ，而[[（（BDI）-B-F3）Mg（mu-OOtBu）]（2）（其中（BDI）-B-F3 = [（ArNCMe）（2）CH]（-）和Ar = C6H2F3- 2,4,6）在类似条件下稳定。观察到的（N，N）MgR型络合物对相应的（N，N）MgOOR烷基过氧化物的选择性氧合与强烈接受的主链金属烷基氧合的自由基链机理相矛盾。此外，观察到烷基过氧化物[（BDI）MgOOBn]（2）转化为醇盐[（BDI）MgOBn]（2）以及在烷基过氧化物[[ （BDI）-B-F3）MgOOtBu]（2）和母体烷基镁[[（（BDI）-B-F3）MgtBu]配合物与醇镁配合物形成是由于两者之间的易位反应导致的常识不符。 MgOOR和Mg-R物种。另外，提出了明确定义的烷基过氧化镁与叔丁基氢过氧化物（TBHP）作为氧源的高催化活性，可用于反查尔酮的环氧化反应。

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