The impact of Metal-Ligand Cooperation in Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium PNP Pincer

被引：134

作者：

Filonenko, Georgy A. ^{[1
,2
]}

Conley, Matthew P. ^{[3
]}

Coperet, Christophe ^{[3
]}

Lutz, Martin ^{[4
]}

Hensen, Emiel J. M. ^{[1
,2
]}

Pidko, Evgeny A. ^{[1
,2
]}

机构：

[1] Eindhoven Univ Technol, Dept Chem Engn, NL-5600 MB Eindhoven, Netherlands

[2] Eindhoven Univ Technol, Inst Complex Mol Syst, NL-5600 MB Eindhoven, Netherlands

[3] ETH, Dept Chem & Appl Biosci, CH-8093 Zurich, Switzerland

[4] Univ Utrecht, Bijvoet Ctr Biomol Res, NL-3584 CH Utrecht, Netherlands

来源：

ACS CATALYSIS | 2013年 / 3卷 / 11期

关键词：

metal-ligand cooperation; ruthenium; CO2; hydrogenation; pincer catalyst; DEFINED IRON CATALYST; FORMIC-ACID; CO2; HYDROGENATION; ALKYL FORMATES; COMPLEXES; ACTIVATION; RU; TRANSFORMATION; CONVERSION; REDUCTION;

D O I：

10.1021/cs4006869

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：

The metal-ligand cooperative activation of CO2 with pyridine-based ruthenium PNP pincer catalysts leads to pronounced inhibition of the activity in the catalytic CO2 hydrogenation to formic acid. The addition of water restores catalytic performance by activating alternative reaction pathways and leads to unprecedented Ru-catalyzed CO2 hydrogenation activity. The mechanism of the underlying chemical transformations is proposed on the basis of DFT calculations, kinetic experiments, and NMR reactivity studies.

引用

页码：2522 / 2526

页数：5

共 51 条

[1] Insertion of CO2 into the Ru-C Bonds of cis- and trans-Ru(dmpe)2Me2 (dmpe = Me2PCH2CH2PMe2) [J].

Allen, Olivia R. ;

Dalgarno, Scott J. ;

Field, Leslie D. ;

Jensen, Paul ;

Willis, Anthony C. .

ORGANOMETALLICS, 2009, 28 (08) :2385-2390

[2] Complexes [(P-2)Rh(hfacac)] as model compounds for the fragment [(P-2)Rh] and as highly active catalysts for CO2 hydrogenation: The accessible molecular surface (AMS) model as an approach to quantifying the intrinsic steric properties of chelating ligands in homogeneous catalysis [J].

Angermund, K ;

Baumann, W ;

Dinjus, E ;

Fornika, R ;

Gorls, H ;

Kessler, M ;

Kruger, C ;

Leitner, W ;

Lutz, F .

CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (05) :755-764

[3]

Aresta M., 2010, CARBON DIOXIDE CHEM

[4]

Balaraman E, 2011, NAT CHEM, V3, P609, DOI [10.1038/NCHEM.1089, 10.1038/nchem.1089]

[5] Pincer CNN Ruthenium(II) Complexes with Oxygen-Containing Ligands (O2CR, OAr, OR, OSiR3, O3SCF3): Synthesis, Structure, and Catalytic Activity in Fast Transfer Hydrogenation [J].

Baratta, Walter ;

Ballico, Maurizio ;

Del Zotto, Alessandro ;

Herdtweck, Eberhardt ;

Magnolia, Santo ;

Peloso, Riccardo ;

Siega, Katia ;

Toniutti, Micaela ;

Zangrando, Ennio ;

Rigo, Pierluigi .

ORGANOMETALLICS, 2009, 28 (15) :4421-4430

[6] Modularly designed transition metal PNP and PCP pincer complexes based on aminophosphines: Synthesis and catalytic applications [J].

Benito-Garagorri, David ;

Kirchner, Karl .

ACCOUNTS OF CHEMICAL RESEARCH, 2008, 41 (02) :201-213

[7] Towards the development of a hydrogen battery [J].

Boddien, Albert ;

Federsel, Christopher ;

Sponholz, Peter ;

Mellmann, Doerthe ;

Jackstell, Ralf ;

Junge, Henrik ;

Laurenczy, Gabor ;

Beller, Matthias .

ENERGY & ENVIRONMENTAL SCIENCE, 2012, 5 (10) :8907-8911

[8] Efficient Dehydrogenation of Formic Acid Using an Iron Catalyst [J].

Boddien, Albert ;

Mellmann, Doerthe ;

Gaertner, Felix ;

Jackstell, Ralf ;

Junge, Henrik ;

Dyson, Paul J. ;

Laurenczy, Gabor ;

Ludwig, Ralf ;

Beller, Matthias .

SCIENCE, 2011, 333 (6050) :1733-1736

[9] Borane-Mediated Carbon Dioxide Reduction at Ruthenium: Formation of C1 and C2 Compounds [J].

Bontemps, Sebastien ;

Vendier, Laure ;

Sabo-Etienne, Sylviane .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2012, 51 (07) :1671-1674

[10] Azaphosphatranes as Structurally Tunable Organocatalysts for Carbonate Synthesis from CO2 and Epoxides [J].

Chatelet, Bastien ;

Joucla, Lionel ;

Dutasta, Jean-Pierre ;

Martinez, Alexandre ;

Szeto, Kai C. ;

Dufaud, Veronique .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (14) :5348-5351

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