Redox-active ligands in catalysis

Luca, Oana R.; Crabtree, Robert H.

doi:10.1039/c2cs35228a

Cited by 937 publications

(584 citation statements)

References 149 publications

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“…An example of such reactivity is given in Section 3.5.3. A topic of interest in the catalysis community, the concept of redox-active actor ligands, plays an important role in CO 2 coordination at metal centers and has been described elsewhere [71]. We give one example of ligand participation in CO 2 binding to the organic fragment of a Ru complex with a redox-active ligand Eq.…”

Section: Lewis-acid/base Activation and Catalysismentioning

confidence: 99%

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

Luca

Fenwick

2015

Journal of Photochemistry and Photobiology B: Biology

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Available online xxxx a b s t r a c tThe present review covers organic transformations involved in the reduction of CO 2 to chemical fuels. In particular, we focus on reactions of CO 2 with organic molecules to yield carboxylic acid derivatives as a first step in CO 2 reduction reaction sequences. These biomimetic initial steps create opportunities for tandem electrochemical/chemical reductions. We draw parallels between long-standing knowledge of CO 2 reactivity from organic chemistry, organocatalysis, surface science and electrocatalysis. We point out some possible non-faradaic chemical reactions that may contribute to product distributions in the production of solar fuels from CO 2 . These reactions may be accelerated by thermal effects such as resistive heating and illumination.

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Section: Lewis-acid/base Activation and Catalysismentioning

confidence: 99%

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

Luca

Fenwick

2015

Journal of Photochemistry and Photobiology B: Biology

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“…This complex also has neutral, radical pyNO • ligands which have N-O distances in the range of 1.298(3)-1.303(2) Å. Similarly, the terbium complex (hfac) 3 Tb(pyNO • ) (Hhfac = 1,1,1,5,5,5-hexafluoropentane-2,4-dione) has a N-O distance of 1.279(9) Å [11] which is significantly shorter than the analogous distance observed for 1. This supports the assignment of fully reduced pyNO − ligands in the gallium complex.…”

Section: Solid-state Theoreticalmentioning

confidence: 99%

“…The synthesis of metal complexes of redox-active and non-innocent ligands is a research area that has been expanding in recent years and has resulted in new classes of complexes for metals from throughout the periodic table [1][2][3][4]. Of specific interest to us is the ability to modulate the reactivity of redox-active ligands through coordination of Lewis acids.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex

et al. 2018

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Abstract:We report the synthesis of a gallium complex incorporating redox-active pyridyl nitroxide ligands. The (pyNO − ) 2 GaCl complex was prepared in 85% yield via a salt metathesis route and was characterized by 1 H and 13 C NMR spectroscopies, X-ray diffraction, and theory. UV-Vis absorption spectroscopy and electrochemistry were used to access the optical and electrochemical properties of the complex, respectively. Our discussion focuses primarily on a comparison of the gallium complex to the corresponding aluminum derivative and shows that although the complexes are very similar, small differences in the electronic structure of the complexes can be correlated to the identity of the metal.

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“…Furthermore, it was possible to reduce the free diborabenzene to its dianion, 1 2-. The stability of 1 in multiple oxidation states promises a rich coordination chemistry, and considering the burgeoning research field of redox-active ligands, [47][48] we are confident that ligand 1 may find applications in homogeneous catalysis.…”

Section: Figurementioning

confidence: 99%

Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η⁶-Diborabenzene Ligand

et al. 2018

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(4)). Investigation of the new complexes with a combination of X-ray diffraction, spectroscopic methods and DFT calculations shows that ligand 1 is a remarkably strong electron donor. In particular, [(η 6 -arene)M(CO) 3 ] complexes of this ligand display the lowest CO stretching frequencies yet observed for this class of complex. Cyclic voltammetry on complexes 2-4 revealed one reversible oxidation and two reversible reduction events in each case, with no evidence of ring-slippage of the arene to the η 4 binding mode. Treatment of 4 with lithium metal in THF led to identification of the paramagnetic complex [(1)W(CO) 3 ]Li·2THF (5). Compound 1 can also be reduced in the absence of a transition metal to its dianion 1 2-, which possesses a quinoid-type structure.

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Redox-active ligands in catalysis

Abstract: Odd-electron, redox-active ligands are discussed in the context of catalysis. We focus on ligandbased, non-singlet state intermediates and their participation in catalytic processes and related stoichiometric transformations.

Cited by 937 publications

References 149 publications

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex

Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η⁶-Diborabenzene Ligand

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Redox-active ligands in catalysis

Abstract: Odd-electron, redox-active ligands are discussed in the context of catalysis. We focus on ligandbased, non-singlet state intermediates and their participation in catalytic processes and related stoichiometric transformations.

Cited by 937 publications

References 149 publications

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

Organic reactions for the electrochemical and photochemical production of chemical fuels from CO2 – The reduction chemistry of carboxylic acids and derivatives as bent CO2 surrogates

Synthesis and Characterization of (pyNO−)2GaCl: A Redox-Active Gallium Complex

Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η6-Diborabenzene Ligand

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Half-Sandwich Complexes of an Extremely Electron-Donating, Redox-Active η⁶-Diborabenzene Ligand