Electrochemical reduction of carbon dioxide catalyzed by [Pd(triphosphine)(solvent)](BF4)2 complexes: synthetic and mechanistic studies

DuBois, Daniel L.; Miedaner, Alex; Haltiwanger, R. C.

doi:10.1021/ja00023a023

Cited by 181 publications

(174 citation statements)

References 0 publications

Supporting

Mentioning

163

Contrasting

Unclassified

Order By: Relevance

“…During CO 2 electrochemical reduction to CO mediated by Pd catalysts, a vacant coordination site facilitates the C-O bond cleavage. 192 This cleavage occurs via migration of a water molecule or hydroxide ion from a metal carboxylate carbon atom to a vacant coordination site on the metal (Scheme 18). In other C-O bond cleavage reactions, formation of MC(O)OM′ linkages or oneelectron M-COOH reduction appears to facilitate C-O bond cleavage.…”

Section: Barriers To Further Progressmentioning

confidence: 99%

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

et al. 2001

Self Cite

View full text Add to dashboard Cite

Section: Barriers To Further Progressmentioning

confidence: 99%

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

et al. 2001

Self Cite

View full text Add to dashboard Cite

“…Essentially the same mechanism was experimentally proposed in the electrochemical reduction of CO 2 to CO catalyzed by a palladium complex. 27 In all these mechanisms, the coordinated CO 2 undergoes protonation and then OH ¹ anion dissociates from CO upon the second one-electron reduction, indicating that the protonation of CO 2 is one crucial step in photo-and electrochemical reductions of CO 2 to CO. Hence, the orbital interaction diagram of Scheme 5 is important for understanding these catalytic reactions and the reason why the protonation is accelerated by the η 1 -C coordination of CO 2 .…”

Section: Introductionmentioning

confidence: 99%

Theoretical and Computational Study of a Complex System Consisting of Transition Metal Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molecular Property, and Reaction Behavior

Sakaki

2015

Bulletin of the Chemical Society of Japan

View full text Add to dashboard Cite

Complex chemical systems consisting of transition metal element(s) are important and attractive research targets in both experimental chemistry and theoretical chemistry. Transition-metal complexes with carbon dioxide are discussed as one example, in which the coordination geometry, bonding nature, and reactivity are understood well and predicted with the HOMO and the number of d electrons. The spin-multiplicity of inverse sandwich-type dinuclear transition-metal complexes, which have been synthesized recently as a new type of compound, is discussed as another example based on CASPT2 calculations, in which the clear relationship between the spin multiplicity of its ground state and the number of d electrons is presented. Theoretical understanding of various organometallic reactions has been an important endeavor over the last two decades. Insertion reactions of olefin and carbon dioxide into MH and Malkyl bonds and σ-bond activation reactions are discussed with orbital interaction diagrams based on perturbation theory. In particular, detailed discussion of the characteristic features of a new type of oxidative addition to an ML moiety (L = neutral ligand such as alkene and alkyne) and heterolytic σ-bond activation by an MX moiety (X = anionic ligand). It is still a central challenge to elucidate the reaction mechanisms of catalytic reactions by transition metal complexes. The reaction mechanisms and electronic processes of Ru-catalyzed hydrogenation of carbon dioxide, Pt-, Rh-, and Zr-catalyzed hydrosilylations of alkene, Ir-catalyzed borylation of benzene, and the Hiyama cross-coupling reaction are analyzed based on computational results. We wish to present how to understand the mechanism based on the number of d electrons and the energy of d orbitals in discussion. Also, the importance of solvation and crystalline effects in the theoretical study of transition-metal complexes is discussed based on our recent theoretical studies of mixed-valence complex and a single crystal of a Pt(II) complex.

show abstract

“…Multiple transition metal catalysts based on Ni [15,16], Fe [17], Re [18], Mn [19], and Pd [20] complexes, for example, have been reported to function as catalysts for electrocatalytic reduction of CO 2 to CO in non-aqueous solvents. Recent developments have led to detailed mechanistic insights and enhanced rates and efficiencies for Re( t Bu-bpy)(CO) 3 Cl ( t BuScheme 4 Strategy for reduction of CO 2 to CO Scheme 5 Hydride insertion strategy for CO 2 reduction to formate Top Catal (2015) 58:30- 45 33 bpy = 4,4 0 -di-tert-butyl-2,2 0 -bipyridine) [21] and Fe porphyrin [22] complexes.…”

Section: Co 2 Reduction By Ru Polypyridyl Complexesmentioning

confidence: 99%

Electrocatalytic Reduction of Carbon Dioxide: Let the Molecules Do the Work

et al. 2014

View full text Add to dashboard Cite

This review summarizes the development of electrochemical CO 2 reduction catalysts in the UNC Energy Frontier Research Center for Solar Fuels. Two strategies for converting CO 2 to CO or formate have been explored. In one, polypyridyl complexes of Ru(II) have been used to reduce CO 2 to CO in acetonitrile and in acetonitrile/water mixtures. In the absence of CO 2 water is reduced to H 2 by these complexes. With added weak acids in acetonitrile with added water and CO 2 , reduction to syngas mixtures of CO and H 2 is observed. A single polypyridyl complex of Ru(II) has been shown to be both a catalyst for water oxidation and CO 2 reduction in an electrochemical cell for CO 2 splitting into CO and O 2 . In parallel, Ir pincer catalysts have been shown to act as selective electrocatalysts for reducing CO 2 to formate in acetonitrile with added water and in pure water without competition from electrocatalytic H 2 production. Details of the catalytic mechanisms of each have also been investigated.The world's energy future is being driven by increased demand which is currently met by increasing use of fossil fuels with their associated environmental impact through the greenhouse gas effect [1]. With technologies that evolve to become cost effective, renewable energy is the appealing energy source of the future with the sun the ultimate energy source. However, large-scale use of solar energy requires large land areas and a vast energy storage capability for nighttime and on-demand utilization. Natural photosynthesis is appealing with energy conversion through stored biomass but, with typical solar efficiencies of B1 %, is impractical as a source for the high energy densities required to power urban centers and industrial complexes. A long-term solution is potentially available based on ''artificial photosynthesis'' with solar fuels the product, water splitting into H 2 and O 2 or reduction of CO 2 to a carbon fuel or carbon fuel precursor [2]. Solar-driven reduction of CO 2 by water occurs in green plants and photosynthetic bacteria and is an inspiration for the development of an artificial photosynthesis-based equivalent. Given the impressive efficiencies reached with current semiconductor technology for photovotaic devices, far higher efficiencies should be reachable in artificial photosynthesis compared to natural photosynthesis with a target of [10 % being a reasonable goal. The products of artificial photosynthesis are so-called solar fuels, highenergy density molecules with solar energy stored in chemical bonds. As noted above, target reactions are water splitting into hydrogen and oxygen, and reduction of CO 2 to CO, formic acid, methanol or other reduced forms of carbon, with hydrocarbons especially attractive because

show abstract

Electrochemical reduction of carbon dioxide catalyzed by [Pd(triphosphine)(solvent)](BF4)2 complexes: synthetic and mechanistic studies

Cited by 181 publications

References 0 publications

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities

Theoretical and Computational Study of a Complex System Consisting of Transition Metal Element(s): How to Understand and Predict Its Geometry, Bonding Nature, Molecular Property, and Reaction Behavior

Electrocatalytic Reduction of Carbon Dioxide: Let the Molecules Do the Work

Contact Info

Product

Resources

About