Pincer Complexes of Palladium- and Nickel-Containing 3-Butyl-1-(1,10-phenanthrolin-2-yl)imidazolylidene as Efficient Aqueous Sonogashira and Kumada Coupling Reactions

Gu, Shaojin; Chen, Wanzhi

doi:10.1021/om801056v

Cited by 138 publications

(58 citation statements)

References 94 publications

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“…The Ni-N and Ni-C bond lengths are within the typical range for these types of donors. 76,[102][103][104] Evaluation of Nickel N-Heterocyclic Carbene-Amine Complexes for Electrocatalytic CO 2 Reduction. The electrochemical behaviors of complexes 1c-4c were interrogated by cyclic voltammetry.…”

Section: Resultsmentioning

confidence: 99%

Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene–Isoquinoline Complex

et al. 2013

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ABSTRACT:The solar-driven reduction of carbon dioxide to value-added chemical fuels is a longstanding challenge in the fields of catalysis, energy science, and green chemistry. In order to develop effective CO 2 fixation, several key considerations must be balanced, including: (1) catalyst selectivity for promoting CO 2 reduction over competing hydrogen generation from proton reduction, (2) visible-light harvesting that matches the solar spectrum, and (3) the use of cheap and earth-abundant catalytic components. In this report, we present the synthesis and characterization of a new family of earthabundant nickel complexes supported by N-heterocyclic carbene-amine ligands that exhibit high selectivity and activity for the electrocatalytic and photocatalytic conversion of CO 2 to CO. Systematic changes in the carbene and amine donors of the ligand have been surveyed, and [Ni( Pr bimiq1)] 2+ (where Pr bimiq1 = bis(3-(imidazolyl)isoquinolinyl)propane, 1c) emerges as a catalyst for electrochemical reduction of CO 2 with the lowest cathodic onset potential (E cat = −1.2 V vs. SCE). Using this earthabundant catalyst with Ir(ppy) 3 (where ppy = 2-phenylpyridine) and an electron donor, we have developed a visible-light photoredox system for the catalytic conversion of CO 2 to CO that proceeds with high selectivity and activity and achieves turnover numbers and turnover frequencies reaching 98,000 and 3.9 s -1 , respectively. Further studies reveal that the overall efficiency of this solar-to-fuel cycle may be limited by the formation of the active Ni catalyst and/or the chemical reduction of CO 2 to CO at the reduced nickel center and provide a starting point for improved photoredox systems for sustainable carbon-neutral energy conversion. 3 IntroductionThe search for sustainable resources has attracted broad interest in the potential use of carbon dioxide as a feedstock for fuels and fine chemicals. [1][2][3][4][5][6][7][8][9][10] In this context, the photocatalytic reduction of CO 2 is an attractive route that can take advantage of the renewable and abundant energy of the sun for longterm CO 2 utilization, 6,11-13 with the eventual target of coupling the reductive half-reaction of CO 2 fixation with a matched oxidative half-reaction such as water oxidation to achieve a carbon-neutral artificial photosynthesis cycle. 14-21 Before this ultimate goal can be realized, however, a host of basic scientific challenges must be addressed, including developing systems that balance selectivity, efficiency, and cost. With regard to selectivity, it is critical to minimize the competitive reduction of water to hydrogen that is typically kinetically favored over CO 2 reduction, as well as selectively convert CO 2 to one carbon product. 22,23 Another primary consideration is the use of visible-light excitation, which more effectively harvests the solar spectrum and avoids deleterious high-energy photochemical pathways. Semiconductors such as TiO 2 and SiC have been widely employed as heterogeneous catalysts for photochemical and photoe...

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Section: Resultsmentioning

confidence: 99%

Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene–Isoquinoline Complex

et al. 2013

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“…Among the various N-heterocyclic carbene ligands reported, functionalized N-heterocyclic carbenes with another donor atom have attracted increasing attention in recent years [1,2,[4][5][6][7][8]. The most well known such ligands are those C,N bidentate ligands with a pyridyl-group as the N-substituent directly attached at the N-heterocycle ring [9,10].…”

Section: Introductionmentioning

confidence: 99%

Synthesis, structure and luminescent properties of rhenium(I) carbonyl complexes containing pyrimidine-functionalized N-heterocyclic carbenes

Wang

Liu

Chen

et al. 2013

Inorganica Chimica Acta

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“…However, deactivated aryl chlorides such as 1-chloro-4-methoxybenzene afforded poor results (20 % yield). [23] Unsymmetrical NHC-based pincer-nickel complexes 24-26 (Scheme 6) are also active catalysts for the cross-coupling of inactivated and deactivated aryl chlorides with aryl Grignard reagents ( Table 5). The reactions proceed smoothly in THF at room temperature.…”

Section: Kumada Reactionsmentioning

confidence: 99%

Nickel‐Catalyzed Cross‐Coupling with Pincer Ligands

Wang

Liu

2012

Eur J Inorg Chem

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Transition‐metal‐catalyzed cross‐coupling reactions are powerful tools for constructing carbon–carbon and carbon–heteroatom bonds. In this microreview we summarize the nickel‐catalyzed cross‐coupling reactions with pincer ligands. The reactions presented here include Kumada, Negishi, Suzuki, and Sonogashira reactions for the formation of different types of C–C bonds, as well as the thiolation of aryl iodides.

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Pincer Complexes of Palladium- and Nickel-Containing 3-Butyl-1-(1,10-phenanthrolin-2-yl)imidazolylidene as Efficient Aqueous Sonogashira and Kumada Coupling Reactions

Cited by 138 publications

References 94 publications

Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene–Isoquinoline Complex

Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N-Heterocyclic Carbene–Isoquinoline Complex

Synthesis, structure and luminescent properties of rhenium(I) carbonyl complexes containing pyrimidine-functionalized N-heterocyclic carbenes

Nickel‐Catalyzed Cross‐Coupling with Pincer Ligands

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