Unusual Tri-, Hexa-, and Nonanuclear Cu(II) Cage Methylsilsesquioxanes: Synthesis, Structures, and Catalytic Activity in Oxidations with Peroxides

被引：56

作者：

Bilyachenko, Alexey N. ^{[1
,2
]}

Kulakova, Alena N. ^{[1
,2
]}

Levitsky, Mikhail M. ^{[1
]}

Petrov, Artem A. ^{[1
]}

Korlyukov, Alexander A. ^{[1
,3
]}

Shul'pina, Lidia S. ^{[1
]}

Khrustalev, Victor N. ^{[1
,2
]}

Dorovatovski, Pavel V. ^{[4
]}

Vologzhanina, Anna V. ^{[1
]}

Tsareva, Ulyana S. ^{[1
]}

Golub, Igor E. ^{[1
,2
]}

Gulyaeva, Ekaterina S. ^{[1
]}

Shubina, Elena S. ^{[1
]}

Shul'pin, Georgiy B. ^{[5
,6
]}

机构：

[1] Russian Acad Sci, Nesmeyanov Inst Organoelement Cpds, Vavilov Str 28, Moscow 119991, Russia

[2] Peoples Friendship Univ Russia, Miklukho Maklay Str 6, Moscow 117198, Russia

[3] Pirogov Russian Natl Res Med Univ, Ostrovitianov Str 1, Moscow 117997, Russia

[4] Kurchatov Inst, Natl Res Ctr, Akad Kurchatova Pl 1, Moscow 123182, Russia

[5] Russian Acad Sci, Semenov Inst Chem Phys, Dom 4, Moscow 119991, Russia

[6] Plekhanov Russian Univ Econ, Dom 36, Moscow 117997, Russia

来源：

INORGANIC CHEMISTRY | 2017年 / 56卷 / 07期

基金：

俄罗斯基础研究基金会;

关键词：

ALKANE OXIDATION; TRANSMETALATION REACTIONS; HYDROCARBON OXYGENATIONS; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURE; METALLASILSESQUIOXANES; FUNCTIONALIZATION; HYDROPEROXIDATION; COMPLEXES; BEHAVIOR;

D O I：

10.1021/acs.inorgchem.7b00061

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Three types of unusual cagelike copper(II) methylsilsesquioxanes, namely, nona- [(MeSiO1.5)(18)(CuO)(9)] 1, hexa- [(MeSiO1.5)(10)(HO0.5)(2)(CuO)(6)(C-12,H8N2)(2)-(MeSiO1.5)(10)(HO0.5)(1.33)(CH3COO0.5)(0.67)(CuO)(6)(Ci(2)H(8)N(2))(2)] 2, (MeSiO1.5)(10)(CuO)(6)(MeO0.5)(2)(C10H8N2)(2)] 3, and trinuclear [(MeSiO1.5)(8)(CUO)(3)(C10H8N2)(2)], 4, were obtained in 44%, 27%, 20%, and 16% yields, respectively. Nuclearity and Structural fashion of products was controlled by the choice of solvent system and ligand, specifically assisting the assembling of cage. Structures of 1-4 were determined by single-crystal X-ray diffraction analysis. Compounds 1 and 4 are the first cage metallasilsesquioxanes, containing nine and three Cu ions, respectively. Product I is the first observation of nonanuclear metallasilsesquioxane ever. Unique architecture of 4 represents early unknown type of molecular geometry, based on,condensed pentamembered siloxane cycles: Topological analysis of metal dusters in products. 1-4 is provided. Complex 1 efficiently catalyzes oxidation of alcohols with tert-butylhydropermade TBHP to ketones or alkanes with H2O2 to alkyl hydroperoxides in acetonitrile.

引用

页码：4093 / 4103

页数：11

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