Effective and Reversible Carbon Dioxide Insertion into Cerium Pyrazolates

被引：49

作者：

Bayer, Uwe ^{[1
]}

Werner, Daniel ^{[1
]}

Maichle-Moessmer, Caecilia ^{[1
]}

Anwander, Reiner ^{[1
]}

机构：

[1] Eberhard Karls Univ Tubingen, Inst Anorgan Chem, Morgenstelle 18, D-72076 Tubingen, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2020年 / 59卷 / 14期

关键词：

carbon dioxide; cerium; cycloaddition; epoxides; pyrazolates; METAL-ORGANIC FRAMEWORK; CYCLOHEXENE OXIDE; ALTERNATING COPOLYMERIZATION; REDUCTIVE DISPROPORTIONATION; STRUCTURAL-CHARACTERIZATION; BETA-DIKETIMINATO; CYCLIC CARBONATES; CO2; INSERTION; COMPLEXES; CAPTURE;

D O I：

10.1002/anie.201916483

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The homoleptic pyrazolate complexes [Ce-4(III)(Me(2)pz)(12)] and [Ce-IV(Me(2)pz)(4)](2) quantitatively insert CO2 to give [Ce-4(III)(Me(2)pzCO(2))(12)] and [Ce-IV(Me(2)pzCO(2))(4)], respectively (Me(2)pz=3,5-dimethylpyrazolato). This process is reversible for both complexes, as observed by in situ IR and NMR spectroscopy in solution and by TGA in the solid state. By adjusting the molar ratio, one molecule of CO2 per [Ce-IV(Me(2)pz)(4)] complex could be inserted to give trimetallic [Ce-3(Me(2)pz)(9)(Me(2)pzCO(2))(3)(thf)]. Both the cerous and ceric insertion products catalyze the formation of cyclic carbonates from epoxides and CO2 under mild conditions. In the absence of epoxide, the ceric catalyst is prone to reduction by the co-catalyst tetra-n-butylammonium bromide (TBAB).

引用

页码：5830 / 5836

页数：7

共 88 条

[1] Tuning Lanthanide Reactivity Towards Small Molecules with Electron-Rich Siloxide Ligands [J].

Andrez, Julie ;

Pecaut, Jacques ;

Bayle, Pierre-Alain ;

Mazzanti, Marinella .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (39) :10448-10452

[2]

[Anonymous], 2014, Angew. Chem. Int. Ed, DOI [DOI 10.1002/ANGE.201309094, 10.1002/ange.201309094]

[3] Catalysis for the Valorization of Exhaust Carbon: from CO2 to Chemicals, Materials, and Fuels. Technological Use of CO2 [J].

Aresta, Michele ;

Dibenedetto, Angela ;

Angelini, Antonella .

CHEMICAL REVIEWS, 2014, 114 (03) :1709-1742

[4] Selective and catalytic carbon dioxide and heteroallene activation mediated by cerium N-heterocyclic carbene complexes [J].

Arnold, Polly L. ;

Kerr, Ryan W. F. ;

Weetman, Catherine ;

Docherty, Scott R. ;

Rieb, Julia ;

Cruickshank, Faye L. ;

Wang, Kai ;

Jandl, Christian ;

McMullon, Max W. ;

Pothig, Alexander ;

Kuehn, Fritz E. ;

Smith, Andrew D. .

CHEMICAL SCIENCE, 2018, 9 (42) :8035-8045

[5] Activation of carbon dioxide and carbon disulfide by a scandium N-heterocyclic carbene complex [J].

Arnold, Polly L. ;

Marr, Isobel A. ;

Zlatogorsky, Sergey ;

Bellabarba, Ronan ;

Tooze, Robert P. .

DALTON TRANSACTIONS, 2014, 43 (01) :34-37

[6] Carbon monoxide and carbon dioxide insertion chemistry of f-block N-heterocyclic carbene complexes [J].

Arnold, Polly L. ;

Turner, Zoee R. ;

Germeroth, Anne I. ;

Casely, Ian J. ;

Nichol, Gary S. ;

Bellabarba, Ronan ;

Tooze, Robert P. .

DALTON TRANSACTIONS, 2013, 42 (05) :1333-1337

[7] Sustainable Conversion of Carbon Dioxide: An Integrated Review of Catalysis and Life Cycle Assessment [J].

Artz, Jens ;

Mueller, Thomas E. ;

Thenert, Katharina ;

Kleinekorte, Johanna ;

Meys, Raoul ;

Sternberg, Andre ;

Bardow, Andre ;

Leitner, Walter .

CHEMICAL REVIEWS, 2018, 118 (02) :434-504

[8] Ce(IV) Complexes with Donor-Functionalized Alkoxide Ligands: Improved Precursors for Chemical Vapor Deposition of CeO2 [J].

Aspinall, Helen C. ;

Bacsa, John ;

Jones, Anthony C. ;

Wrench, Jacqueline S. ;

Black, Kate ;

Chalker, Paul R. ;

King, Peter J. ;

Marshall, Paul ;

Werner, Matthew ;

Davies, Hywel O. ;

Odedra, Rajesh .

INORGANIC CHEMISTRY, 2011, 50 (22) :11644-11652

[9] Solution structures of alkali metal cyclopentadienides in THF estimated by ECC-DOSY NMR-spectroscopy (incl. software) [J].

Bachmann, Sebastian ;

Gernert, Bjoern ;

Stalke, Dietmar .

CHEMICAL COMMUNICATIONS, 2016, 52 (87) :12861-12864

[10] Reaction of a tetranuclear N,N-di-iso-propylcarbamato complex of cerium(III) with dioxygen:: synthesis and X-ray characterization of both the oxidation product and its precursor [J].

Baisch, U ;

Dell' Amico, DB ;

Calderazzo, F ;

Labella, L ;

Marchetti, F ;

Vitali, D .

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 2003, 204 :259-265

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