Gold(III) Olefin Complexes

Savjani, Nicky; Roşca, Dragoş‐Adrian; Schormann, Mark; Bochmann, Manfred

doi:10.1002/anie.201208356

Cited by 87 publications

(99 citation statements)

References 79 publications

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“…[5,6] Elucidating the reaction chemistry of gold(III) has provided major challenges and has highlighted that drawing mechanistic analogies between gold(III) and the isolectronic Pd and Pt systems is often not valid. [7][8][9] We show herein that the hitherto elusive Au III alkyne complexes can in fact readily be generated and have Aualkyne bond energies comparable to those of platinum, but are drastically more reactive. [9a] (2; Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

et al. 2017

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Abstract:The synthesis and characterization of hitherto hypothetical Au III p-alkyne complexes is reported. Bonding and stability depend strongly on the trans effect and steric factors.B onding characteristics shed light on the reasons for the very different stabilities between the classical alkyne complexes of Pt II and their drastically more reactive Au III congeners.L ack of back-bonding facilitates alkyne slippage, which is energetically less costly for gold than for platinum and explains the propensity of gold to facilitate C À Cb ond formation. Cycloaddition followed by aryl migration and reductive deprotonation is presented as an ew reaction sequence in gold chemistry.

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Section: Introductionmentioning

confidence: 99%

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

et al. 2017

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“…[2][3][4][5][6][7][8] However, there are only scarce reports of Au(III)-mediated functionalization of the simplest olefin, ethylene. 9 More recently, Bochmann and co-workers (Scheme 1, bottom) 10 showed that ethylene slowly undergoes a formal insertion into the Au-OAc F bond trans to the pyridine-N in a diarylpyridine CNC pincer complex to yield an Au(III) acetoxyalkyl complex (OAc F = OCOCF 3 ). Reactions of ethylene and propylene with HAuCl 3 and AuCl 3 (tppts) (tppts = 3,3′,3″-phosphanetriyltris-(benzenesulfonic acid) trisodium salt) led to Au(III) hydroxyalkyl species, which upon heating underwent gold reduction to the metal with concomitant formation of organic oxygenated products (alcohols, aldehyde or ketone).…”

Section: Introductionmentioning

confidence: 99%

Small-molecule activation at Au(iii): metallacycle construction from ethylene, water, and acetonitrile

et al. 2016

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Incorporation of the simple, readily available, building blocks ethylene, water and acetonitrile into Au(tpy)(OCOCF3)2 (tpy = 2-(p-tolyl)pyridine) in a one-step reaction leads to high yields of a new 6-membered ring gold(iii) metallacycle complex. The metallacycle has been characterized spectroscopically and crystallographically, and the mechanism of its formation has been investigated with the aid of DFT calculations.

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“…We found recently that C^N^C pincer ligands based on the dianionic 2,6-diphenylpyridine framework are capable of stabilizing a number of novel gold(III) compound types 32,33 , including the first examples of gold(III) hydrides and olefin complexes 34,35 . Given the importance of oxygen ligands in oxidations as well as water cleavage reactions, we decided to explore the reactivity of such gold(III) pincer complexes towards oxygen ligands, including possible Au-O2Au-H interconversions.…”

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confidence: 99%

Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

et al. 2013

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Gold catalysts are widely studied in chemical and electrochemical oxidation processes. Computational modelling has suggested the participation of Au-OO-Au, Au-OOH or Au-OH surface species, attached to gold in various oxidation states. However, no structural information was available as isolable gold peroxo and hydroperoxo compounds were unknown. Here we report the syntheses, structures and reactions of a series of gold(III) peroxides, hydroperoxides and alkylperoxides. The Au-O bond energy in peroxides is weaker than in oxides and hydroxides; however, the Au-OH bond is also weaker than Au-H. Consequently Au-OH compounds are capable of oxygen-transfer generating gold hydrides, a key reaction in a water splitting cycle and an example that gold can react in a way that other metals cannot. For the first time it has become possible to establish a direct connection from peroxides to hydrides: Au-OO-Au-Au-OOH-Au-OH-Au-H, via successive oxygen-transfer events.

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Gold(III) Olefin Complexes

Cited by 87 publications

References 79 publications

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

Gold(III) Alkyne Complexes: Bonding and Reaction Pathways

Small-molecule activation at Au(iii): metallacycle construction from ethylene, water, and acetonitrile

Gold peroxide complexes and the conversion of hydroperoxides into gold hydrides by successive oxygen-transfer reactions

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