Bilyachenko Alexey N, Khrustalev Victor N, Dorovatovskii Pavel V, Shul'pina Lidia S, Ikonnikov Nikolay S, Shubina Elena S, Lobanov Nikolai N, Aliyeva Vusala A, Nunes Ana V M, Mahmudov Kamran T, Kozlov Yuriy N, Pombeiro Armando J L
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Street, Moscow 119991, Russian Federation.
Peoples' Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya Street, Moscow 117198, Russian Federation.
Inorg Chem. 2024 Jan 29;63(4):1909-1918. doi: 10.1021/acs.inorgchem.3c03587. Epub 2024 Jan 12.
Unprecedented iron-based silsesquioxane/acetylacetonate complexes were synthesized. The intriguing cage-like structure of compounds is alkaline metal-dependent: the FeLi complex includes condensed Si-silsesquioxane and four acetylacetonate ligands; the FeNa complex exhibits two cyclic Si-silsesquioxane and eight acetylacetonate ligands, while the FeK complex features two cyclic Si-silsesquioxane and six acetylacetonate ligands. The latter case is the very first observation of small trimeric silsesquioxane ligands in the composition of cage-like metallasilsesquioxanes. The FeNa-based complex exhibits a record high activity in the oxidation of inert alkanes with peroxides (55% yield of oxygenates in cyclohexane oxidation). It also acts as a catalyst in the cycloaddition of CO with epoxides, leading to cyclic carbonates in good yields (58-96%).
合成了前所未有的铁基倍半硅氧烷/乙酰丙酮配合物。这些化合物有趣的笼状结构取决于碱金属：FeLi配合物包含缩合的Si-倍半硅氧烷和四个乙酰丙酮配体；FeNa配合物呈现两个环状Si-倍半硅氧烷和八个乙酰丙酮配体，而FeK配合物具有两个环状Si-倍半硅氧烷和六个乙酰丙酮配体。后一种情况是首次在笼状金属倍半硅氧烷的组成中观察到小三聚体倍半硅氧烷配体。基于FeNa的配合物在过氧化物氧化惰性烷烃反应中表现出创纪录的高活性（环己烷氧化中含氧化合物产率为55%）。它还可作为CO与环氧化物环加成反应的催化剂，以良好的产率（58 - 96%）生成环状碳酸酯。
