Ionic Complexes of Tetra- and Nonanuclear Cage Copper(II) Phenylsilsesquioxanes: Synthesis and High Activity in Oxidative Catalysis

被引：33

作者：

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

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

Levitsky, Mikhail M. ^{[1
]}

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

Khrustalev, Victor N. ^{[2
]}

Vologzhanina, Anna V. ^{[1
]}

Titov, Aleksei A. ^{[1
,2
]}

Dorovatovskii, Pavel V. ^{[4
]}

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

Lamaty, Frederic ^{[5
]}

Bantreil, Xavier ^{[5
]}

Villemejeanne, Benoit ^{[5
]}

Ruiz, Cindy ^{[5
]}

Martinez, Jean ^{[5
]}

Shubina, Elena S. ^{[1
]}

Shul'pin, Georgiy B. ^{[6
,7
]}

机构：

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

[2] RUDN Univ, 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 123098, Russia

[5] Univ Montpellier, IBMM, UMR 5247, CNRS,ENSCM, Site Triolet,Pl Eugene Bataillon, F-34095 Montpellier 5, France

[6] Russian Acad Sci, Semenov Inst Chem Phys, Ulitsa Kosygina 4, Moscow 119991, Russia

[7] Plekhanov Russian Univ Econ, Stremyannyi Pereulok 36, Moscow 117997, Russia

来源：

CHEMCATCHEM | 2017年 / 9卷 / 23期

基金：

俄罗斯基础研究基金会;

关键词：

amides; cage compounds; copper; oxidation; synthesis design; HYDROGEN-PEROXIDE; STRUCTURAL-CHARACTERIZATION; HYDROCARBON OXYGENATIONS; SILSESQUIOXANE SYNTHESIS; COORDINATION POLYMERS; AEROBIC OXIDATION; BENZYL ALCOHOLS; X-RAY; IRON; FUNCTIONALIZATION;

D O I：

10.1002/cctc.201701063

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

Herein, we describe an approach to cage metallasilsesquioxanes by self-assembly with 1,2-bis(diphenylphosphino)ethane as a key reactant. This approach allowed us to achieve a unique family of complexes that includes anionic tetra- and nonanuclear cage copper(II) sodium silsesquioxane and cationic copper(I) 1,2-bis(diphenylphosphino)ethane components. Additional representatives of this intriguing metallasilsesquioxane family (Cu9Na6 and Cu9Na3Cs3) were obtained through the replacement of the original ethanol-based reaction medium by DMSO. The fascinating structural peculiarities of all products were established by using XRD and topological studies. Initial tests for the application of the synthesized complexes as catalysts revealed their very high activity in the homogeneous oxidation of alkanes and alcohols to produce alkyl hydroperoxides, ketones, and amides.

引用

页码：4437 / 4447

页数：11

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