Despite considerable progress in the multifaceted chemistry of non-redox-metal alkylperoxides, the knowledge about magnesium alkylperoxides is in its infancy and only started to gain momentum. Harnessing the well-defined dimeric magnesium tert-butylperoxide [(^f5BDI)Mg(μ-η²:η¹-OOtBu)]₂ incorporating a fluorinated β-diketiminate ligand, herein, we demonstrate its transformation at ambient temperature to a spiro-type, tetranuclear magnesium alkylperoxide [(^f5BDI)₂Mg₄(μ-OOtBu)₆]. The latter compound was characterized by single-crystal X-ray diffraction and its molecular structure can formally be considered as a homoleptic magnesium tert-butylperoxide [Mg(µ-OOtBu)₂]₂ terminated by two monomeric magnesium tert-butylperoxides. The formation of the tetranuclear magnesium alkylperoxide not only contradicts the notion of the high instability of magnesium alkylperoxides, but also highlights that there is much to be clarified with respect to the solution behaviour of these species. Finally, we probed the reactivity of the dimeric alkylperoxide in model oxygen transfer reactions like the commonly invoked metathesis reaction with the parent alkylmagnesium and the catalytic epoxidation of trans-chalcone with tert-butylhydroperoxide as an oxidant. The results showed that the investigated system is among the most active known catalysts for the epoxidation of enones.

尽管在非氧化还原金属烷基过氧化物的多方面化学方面取得了相当大的进展，但对烷基过氧化物镁的了解还处于起步阶段，并且才刚刚开始获得动力。利用定义明确的二聚叔丁基过氧化镁 [( ^f5 BDI​​)Mg(μ-η ² :η ¹ -OO t Bu)] ₂结合氟化 β-二酮亚胺配体，我们在本文中展示了它在环境温度下转化为螺型四核烷基过氧化镁 [( ^f5 BDI​​) ₂ Mg ₄ (μ-OO t Bu) ₆]. 后一种化合物的特征在于单晶 X 射线衍射，其分子结构可以形式上被认为是均配的叔丁基过氧化镁 [Mg(µ-OO t Bu) ₂ ] ₂由两个单体叔丁基过氧化镁封端。四核烷基过氧化镁的形成不仅与烷基过氧化镁的高度不稳定性的概念相矛盾，而且突出表明关于这些物种的溶液行为还有很多需要澄清的地方。最后，我们探讨了二聚烷基过氧化物在模型氧转移反应中的反应性，例如通常调用的与母体烷基镁的复分解反应和催化环氧化以叔丁基氢过氧化物为氧化剂的反式查耳酮。结果表明，所研究的系统是已知最活跃的烯酮环氧化催化剂之一。