Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

Schneck, Felix; Schendzielorz, Florian; Hatami, Nareh; Finger, Markus; Würtele, Christian; Schneider, Sven

doi:10.1002/anie.201803396

Cited by 26 publications

(20 citation statements)

References 43 publications

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“…Bearing in mind that not many Ni II ‐CO complexes are known to date, [25, 28–39] due to the limited ability of Ni II to stabilize such entities via backbonding, we next tested whether a Ni II ‐CO complex with the L t Bu− ligand system would be stable at all and reacted the cationic complex [L t Bu Ni II (OH 2 )][B(Ar F ) 4 ] ( 2 , see S3) with CO gas. A change of color from green to purple could be observed, and evaporation of all volatiles left behind a purple solid.…”

Section: Resultsmentioning

confidence: 99%

“…Bearing in mind that not many Ni II -CO complexes are known to date, [25,[28][29][30][31][32][33][34][35][36][37][38][39] due to the limited ability of Ni II to stabilize such entities via backbonding,w en ext tested whether aN i II -CO complex with the L tBuÀ ligand system would be stable at all and reacted the cationic complex (Figure 2). Thestructure determination further revealed that one of the aryl rings of L tBu undergoes an h 2 coordination, thus completing as quare planar coordination sphere of the Ni center,w hich also reflects in ad iamagnetic 1 HNMR spectrum of as olution of 3 in CD 2 Cl 2 .…”

Section: à -Liberation Of Comentioning

confidence: 99%

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Selective Transformation of Nickel‐Bound Formate to CO or C−C Coupling Products Triggered by Deprotonation and Steered by Alkali‐Metal Ions

Zimmermann

Rößler

et al. 2020

Angewandte Chemie

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The complexes [LtBuNi(OCO‐κ2O,C)]M3[N(SiMe3)2]2 (M=Li, Na, K), synthesized by deprotonation of a nickel formate complex [LtBuNiOOCH] with the corresponding amides M[N(SiMe3)2], feature a NiII−CO22− core surrounded by Lewis‐acidic cations (M+) and the influence of the latter on the behavior and reactivity was studied. The results point to a decrease of CO2 activation within the series Li, Na, and K, which is also reflected in the reactivity with Me3SiOTf leading to the liberation of CO and formation of a Ni−OSiMe3 complex. Furthermore, in case of K+, the {[K3[N(SiMe3)2]2}+ shell around the Ni−CO22− entity was shown to have a large impact on its stabilization and behavior. If the number of K[N(SiMe3)2] equivalents used in the reaction with [LtBuNiOOCH] is decreased from 3 to 0.5, the deprotonated part of the precursor enters a complex reaction sequence with formation of [LtBuNiI(μ‐OOCH)NiILtBu]K and [LtBuNi(C2O4)NiLtBu]. The same reaction at higher concentrations additionally led to the formation of a unique hexanuclear NiII complex containing both oxalate and mesoxalate ([O2C‐CO2‐CO2]4−) ligands.

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Section: Resultsmentioning

confidence: 99%

Section: à -Liberation Of Comentioning

confidence: 99%

Selective Transformation of Nickel‐Bound Formate to CO or C−C Coupling Products Triggered by Deprotonation and Steered by Alkali‐Metal Ions

Zimmermann

Rößler

et al. 2020

Angewandte Chemie

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“…Thermolcatalytic CO 2 conversion to hydrocarbons typically involves two pathways: the modified FT and methanol‐ and DME‐mediated synthesis routes, which are distinguished by their intermediates. The modified FT synthesis comprises CO 2 hydrogenation to CO intermediates via the reverse water‐gas shift (RWGS) reaction [Equation ()], [ 50 ] followed by CO hydrogenation to hydrocarbons via FT synthesis [Equation ()]. [ 1,51 ] The methanol and DME‐mediated synthesis routes are composed of CO 2 conversion to methanol and DME intermediates that further undergo methanol‐ and DME‐to‐hydrocarbon processes [ 52 ]

{CO}_{2} + H_{2} ⇌ CO + H_{2} O, Δ H_{25 ° C} = 41.2 kJ {mol}^{- 1}

n CO + 2 n H_{2} ⇌ C_{n} H_{2 n} + n H_{2} O

…”

Section: Co2 Conversion Over Zeolite‐based Catalystsmentioning

confidence: 99%

Applications of Zeolites to C1 Chemistry: Recent Advances, Challenges, and Opportunities

2020

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However, due to growing concerns regarding crude oil depletion and increasing environmental requirements, finding abundant fossil hydrocarbons with high H 2 /C ratios as well as alternative carbon resources has become crucial to maintaining sustainable, environmentally benign systems that can aid human development. [2] Thus, one-carbon (C1) chemistry, which is the chemistry of C1 molecules that can be derived from sources other than fossil hydrocarbons, including carbon monoxide (CO), carbon dioxide (CO 2), methane (CH 4), methanol (CH 3 OH), and formic acid (HCOOH), has emerged and plays important roles in the energy supply and high-value chemical preparation. [1,3] These C1 resources can be obtained from natural gas, shale gas, coal, biomass, solid wastes, and CO 2 emissions. [3a,4] Extensive studies have been dedicated to the catalytic conversion of C1 molecules, including production of dimethyl ether (DME) and liquid fuels from syngas (a mixture of CO and H 2); production of methanol, light olefins, and even aromatics from CH 4 ; and production of hydrogen from HCOOH. [5] All of these transformations require metallic catalytic species such as single atoms; clusters; or oxides, carbides, or alloy particles (e.g., Rh-, AuPd-, Fe 3 O 4-, and Fe 5 C 2-based catalysts). However, these isolated metallic species suffer from severe sintering due to a lack of confinement effects from supports, which leads to poor catalytic stability and decreased selectivities toward their target products. The efficient production of a specific range of hydrocarbons or oxygenates remains a difficult scientific and technical challenge. Overcoming product selectivity limitations and improving catalyst stabilities via catalyst designs are important areas of research. Zeolites are an important class of shape-selective catalysts with uniform micropores, tunable acidities, and high thermal and hydrothermal stabilities. Over the past decade, they have gained broad popularity and been applied to various industrially important catalytic processes. [6] In particular, the design and development of zeolite-based mono-, bi-, and multifunctional catalysts that combine the advantages of zeolites with those of metallic catalytic species have boosted the application of zeolites to C1 chemistry. As shown in Figure 1, value-added hydrocarbons and oxygenates can be produced from C1 molecules via various catalytic routes over zeolite-based catalysts. By May of 2020, the Structure Commission of the International C1 chemistry, which is the catalytic transformation of C1 molecules including CO, CO 2 , CH 4 , CH 3 OH, and HCOOH, plays an important role in providing energy and chemical supplies while meeting environmental requirements. Zeolites are highly efficient solid catalysts used in the chemical industry. The design and development of zeolite-based mono-, bi-, and multifunctional catalysts has led to a booming application of zeolite-based catalysts to C1 chemistry. Combining the advantages of zeolites and metallic catalytic species has promoted the catal...

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“…Similarities and differences between the two proposed catalytic systems for CO hydrogenation can be found in Scheme 57; it is possible to observe how the method proposed by Beller is superior in terms of hydrogen pressure, catalyst loading, as well as reaction time. In 2018, Schneider proposed a reverse water-gas-shift reaction (WGS) promoted by a nickel pincer complex at ambient reaction conditions [617]. The authors proposed a novel mechanism for In 2018, Schneider proposed a reverse water-gas-shift reaction (WGS) promoted by a nickel pincer complex at ambient reaction conditions [617].…”

Section: Co 2 Hydrogenation To Methanolmentioning

confidence: 99%

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

2020

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Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has the potential to play a fundamental role in this process, providing novel, efficient, and at the same time eco-friendly routes for both chemicals and energy production. In particular, pincer-type ligation shows promising properties in terms of long-term stability and selectivity, as well as allowing for mild reaction conditions and low catalyst loading. Indeed, pincer complexes have been applied to a plethora of sustainable chemical processes, such as hydrogen release, CO2 capture and conversion, N2 fixation, and biomass valorization for the synthesis of high-value chemicals and fuels. In this work, we show the main advances of the last five years in the use of pincer transition metal complexes in key catalytic processes aiming for a more sustainable chemical and energy production.

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Photochemically Driven Reverse Water‐Gas Shift at Ambient Conditions mediated by a Nickel Pincer Complex

Cited by 26 publications

References 43 publications

Selective Transformation of Nickel‐Bound Formate to CO or C−C Coupling Products Triggered by Deprotonation and Steered by Alkali‐Metal Ions

Selective Transformation of Nickel‐Bound Formate to CO or C−C Coupling Products Triggered by Deprotonation and Steered by Alkali‐Metal Ions

Applications of Zeolites to C1 Chemistry: Recent Advances, Challenges, and Opportunities

Recent Progress with Pincer Transition Metal Catalysts for Sustainability

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