Bilyachenko Alexey N, Khrustalev Victor N, Arteev Ivan S, Shul'pina Lidia S, Ikonnikov Nikolay S, Kirillova Marina V, Shubina Elena S, Kirillov Alexander M, Kozlov Yuriy N, Lobanov Nikolai N, Ragimov Karim G, Sun Di
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, Vavilov Street 28, 119991 Moscow, Russia.
Peoples' Friendship University of Russia (RUDN University), Miklukho-Maklay Str. 6, 117198 Moscow, Russia.
Inorg Chem. 2024 Oct 28;63(43):20404-20414. doi: 10.1021/acs.inorgchem.4c02806. Epub 2024 Oct 15.
We report a high nuclear (Cu) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic Cu(dppe) moieties and an anionic silsesquioxane cage of an unprecedented Cu structural type. The Cu cage fragment exhibits a unique () combination of Si-cyclic/Si-acyclic silsesquioxane ligands and () encapsulation of two different chloride and carbonate species. This complex acts as a promising precatalyst in the mild oxidation and carboxylation of light alkanes to produce alkyl hydroperoxides, alcohols, ketones, or carboxylic acids. The present study widens the family of copper-methylsilsesquioxane clusters with prospective use in oxidation catalysis.
我们报道了一种通过铜-甲基倍半硅氧烷与1,2-双（二苯基膦基）乙烷（dppe）络合诱导自组装合成的高核（铜）配合物。该结构包括两个阳离子Cu(dppe)部分和一个前所未有的铜结构类型的阴离子倍半硅氧烷笼。铜笼片段表现出硅环/硅非环倍半硅氧烷配体的独特（）组合以及两种不同氯化物和碳酸盐物种的（）封装。这种配合物在轻质烷烃温和氧化和羧化以生产烷基氢过氧化物、醇、酮或羧酸方面是一种有前景的预催化剂。本研究拓宽了在氧化催化中具有潜在用途的铜-甲基倍半硅氧烷簇家族。
