A dinuclear silver hydride and an umpolung reaction of CO2

Tate, Brandon K.; Wyss, Chelsea M.; Bacsa, John; Kluge, Kelly A.; Gelbaum, Leslie T.; Sadighi, Joseph P.

doi:10.1039/c3sc50896j

Cited by 63 publications

(58 citation statements)

References 108 publications

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“…[178] The core of these complexes adopt a triangular structure, with a silverÀsilver distance shorter than that of silver metal. [178] The core of these complexes adopt a triangular structure, with a silverÀsilver distance shorter than that of silver metal.…”

Section: Scheme 14mentioning

confidence: 99%

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

2014

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In the last two decades, CO2 emission has caused a lot of environmental problems. To mitigate the concentration of CO2 in the atmosphere, various strategies have been implemented, one of which is the use of N-heterocyclic carbenes (NHCs) and related complexes to accomplish the capture, fixation, and activation of CO2 effectively. In this review, we summarize CO2 capture, fixation, and activation by utilizing NHCs and related complexes; homogeneous reactions and their reaction mechanisms are discussed. Free NHCs and NHC salts can capture CO2 in both direct and indirect ways to form imidazolium carboxylates, and they can also catalyze the reaction of aromatic aldehydes with CO2 to form carboxylic acids and derivatives. Moreover, associated with transition metals (TMs), NHCs can form NHC-TM complexes to transform CO2 into industrial acid or esters. Non-metal-NHC complexes can also catalyze the reactions of silicon and boron complexes with CO2 . In addition, catalytic cycloaddition of epoxides with CO2 is another effective function of NHC complexes, and NHC ionic liquids perform excellently in this aspect.

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Section: Scheme 14mentioning

confidence: 99%

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

2014

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“…Silver hydrides are key intermediates in a number of reactions involving organic substrates5 and several silver hydrides have been recently isolated and structurally characterised by X‐ray crystallography 6. In one such study, hydrogen evolution from [(LAg) 2 H] + (where L=N‐heterocyclic carbene ligand 1,3‐bis(2,6‐diisopropylphenyl)imidazolin‐2‐ylidene) was observed, but the precise mechanism for H 2 formation is unknown 6e. Gas‐phase studies on mass selected silver hydride clusters allow their structure7 and reactivity8 to be directly probed.…”

Section: Introductionmentioning

confidence: 99%

Formation and Characterisation of the Silver Hydride Nanocluster Cation [Ag₃H₂((Ph₂P)₂CH₂)]⁺ and Its Release of Hydrogen

Girod

Krstić

Antoine

et al. 2014

Chemistry A European J

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Multistage mass spectrometry and density functional theory (DFT) were used to characterise the small silver hydride nanocluster, [Ag3 H2 L](+) (where L=(Ph2 P)2 CH2 ) and its gas-phase unimolecular chemistry. Collision-induced dissociation (CID) yields [Ag2 HL](+) as the major product while laser-induced dissociation (LID) proceeds via H2 formation and subsequent release from [Ag3 H2 L](+) , giving rise to [Ag3 L](+) as the major product. Deuterium labelling studies on [Ag3 D2 L](+) prove that the source of H2 is from the hydrides and not from the ligand. Comparison of TD-DFT absorption patterns obtained for the optimised structures with action spectroscopy results, allows assignment of the measured features to structures of precursors and products. Molecular dynamics "on the fly" reveal that AgH loss is favoured in the ground state, but H2 formation and loss is preferred in the first excited state S1 , in agreement with CID and LID experimental findings. This indicates favourable photo-induced formation of H2 and subsequent release from [Ag3 H2 L](+) , an important finding in context of metal hydrides as a hydrogen storage medium, which can subsequently be released by heating or irradiation with light.

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“…[9,10] There is,h owever, ag rowing appreciation that species possessing three-center,two-electron M À H À Mb onds may play ar ole in catalysis.F or example,L alic and coworkers have shown that cationic dinuclear copper(I) hydride complexes are key catalytic intermediates in the hydroalkoxylation of alkynes. [12,13] Despite detailed studies on the preparation and reactivity of symmetric dinuclear coinage metal hydrides,little is known about heterobimetallic compounds with asymmetric MÀHÀ M' moieties.C ombinations of copper and gold NHC complexes catalyze the addition of phenols to internal alkynes with activities that are greater than the individual components of the mixture. [12,13] Despite detailed studies on the preparation and reactivity of symmetric dinuclear coinage metal hydrides,little is known about heterobimetallic compounds with asymmetric MÀHÀ M' moieties.C ombinations of copper and gold NHC complexes catalyze the addition of phenols to internal alkynes with activities that are greater than the individual components of the mixture.…”

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confidence: 99%

Selective Reduction of CO₂ to a Formate Equivalent with Heterobimetallic Gold‐ ‐ ‐Copper Hydride Complexes

2017

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A series of heterobimetallic complexes containing three-center, two-electron Au-H-Cu bonds have been prepared from addition of a parent gold hydride to a bent d copper(I) fragment. These highly unusual heterobimetallic complexes represent a missing link in the widely investigated series of neutral and cationic coinage metal hydride complexes containing Cu-H-Cu and M-H-M moieties (M=Cu, Ag). The well-defined heterobimetallic hydride complexes act as precatalysts for the conversion of CO into HCO Bpin with HBpin as the reductant. The selectivity of the heterobimetallic complexes for the catalytic production of a formate equivalent surpasses that of the parent monomeric Group 11 complexes.

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A dinuclear silver hydride and an umpolung reaction of CO2

Cited by 63 publications

References 108 publications

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

Formation and Characterisation of the Silver Hydride Nanocluster Cation [Ag₃H₂((Ph₂P)₂CH₂)]⁺ and Its Release of Hydrogen

Selective Reduction of CO₂ to a Formate Equivalent with Heterobimetallic Gold‐ ‐ ‐Copper Hydride Complexes

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A dinuclear silver hydride and an umpolung reaction of CO2

Cited by 63 publications

References 108 publications

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes

Formation and Characterisation of the Silver Hydride Nanocluster Cation [Ag3H2((Ph2P)2CH2)]+ and Its Release of Hydrogen

Selective Reduction of CO2 to a Formate Equivalent with Heterobimetallic Gold‐ ‐ ‐Copper Hydride Complexes

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Formation and Characterisation of the Silver Hydride Nanocluster Cation [Ag₃H₂((Ph₂P)₂CH₂)]⁺ and Its Release of Hydrogen

Selective Reduction of CO₂ to a Formate Equivalent with Heterobimetallic Gold‐ ‐ ‐Copper Hydride Complexes