Highly Selective Acylation of Dimethylamine Mediated by Oxygen Atoms on Metallic Gold Surfaces

Xu, Bingjun; Zhou, Ling; Madix, Robert J.; Friend, Cynthia M.

doi:10.1002/ange.200905642

Cited by 24 publications

(11 citation statements)

References 31 publications

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“…Madix et al were the first to show that oxygen bound to Group 11 transition metal (Cu and Ag) surfaces behaves as a Brønsted base and promotes the activation of strong but acidic O-H bonds in water [22,23], methanol [24][25][26], ethanol [27], formic acid [28][29][30] and acetic [31] acid, as well as acidic C-H bonds of acetylene [32,33] and propylene [34]. Later work expanded these ideas from the promotional effects of O* on Cu and Ag to Au surfaces involved in the oxidation and coupling of alcohols [15,[35][36][37][38][39][40][41], oxidation of alkenes [42], and oxidative dehydrogenation of acids [43][44][45][46][47]. Similar results show that O* can also act as a Brønsted base and promote the oxidation of alcohols and the decomposition of organic acids over specific non-noble metal Pd [48][49][50][51][52] and Pt [53] surfaces.…”

Section: Introductionmentioning

confidence: 99%

Promotional effects of chemisorbed oxygen and hydroxide in the activation of C–H and O–H bonds over transition metal surfaces

Hibbitts

Neurock

2016

Surface Science

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Section: Introductionmentioning

confidence: 99%

Promotional effects of chemisorbed oxygen and hydroxide in the activation of C–H and O–H bonds over transition metal surfaces

Hibbitts

Neurock

2016

Surface Science

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“…We will do this from a theoretical perspective, but it is important to stress that it is a close coupling between theory and experiment which has enabled the developments thus far. Surface science experiments have been invaluable in providing a quantitative description of a range of surface phenomena (5)(6)(7)(8)(9)(10)(11)(12)(13)(14). This has been essential in benchmarking computational surface science based on density functional theory (DFT) calculations and in providing experimental guidance and verification of the concepts developed.…”

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confidence: 99%

Density functional theory in surface chemistry and catalysis

Nørskov

Abild‐Pedersen

Studt

et al. 2011

Proc. Natl. Acad. Sci. U.S.A.

1,889

1,342

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Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future challenges. S urface chemistry is interesting and challenging for several reasons. It takes place at the border between the solid state and the liquid or gas phase and can be viewed as a meeting place between condensed-matter physics and chemistry. The phenomena at the solid-gas or solid-liquid interface are complicated for this reason. A chemical reaction at a metal surface, for instance, has all of the complexity of ordinary gas-phase reactions, but in addition the usual electron conservation rules do not apply because the metal provides a semi-infinite source of electrons at the Fermi level. A new set of concepts therefore needs to be developed to describe surface chemistry.An understanding of surface chemical reactions is necessary to describe a large number of surface phenomena including semiconductor processing, corrosion, electrochemistry, and heterogeneous catalysis. Heterogeneous catalysis alone has been estimated to be a prerequisite for more than 20% of all production in the industrial world (1), and it will most likely gain further importance in the years to come. The development of sustainable energy solutions represents one of the most important scientific and technical challenges of our time, and heterogeneous catalysis is at the heart of the problem. Most sustainable energy systems rely on the energy influx from the sun. Sunlight is diffuse and intermittent, and it is therefore essential to be able to store the energy, for example chemically as a fuel or in a battery. Such storage can then provide energy for the transportation sector and in decentralized applications, as it evens out temporal variations (2, 3). The key to providing an efficient transformation of energy to a chemical form or from one chemical form into another is the availability of suitable catalysts. In essentially all possible sustainable energy technologies, the lack of efficient and economically viable catalysts is a primary factor limiting their use (3, 4).In the present paper, we will discuss the status of the development of an understanding of surface chemistry. We will do this from a theoretical perspective, but it is important to stress that it is a close coupling between theory and experiment which has enabled the developments thus far. Surface science experiments have been invaluable in providing a quantitative description of a range of surface phenomena (5-14). This has been essential in benchmarking computational surface science based on density functional theory (DFT) calculations and in providing experimental guidance and verification of the concepts developed. This forms a good background for the development of an understanding of heterogeneous catalysis, which is the other part of this paper. We will show how the concepts dev...

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“…Gold is of interest because of its high activity and selectivity for a broad range of molecular transformations at low temperature on both single crystal models and on working catalysts, , including partial oxidation of alkenes, , and selective oxidation and oxidative coupling of alcohols. , Gold has been found to be active for oxygen-assisted coupling of methanol with alcohols, ,− CO, and amines − to form methyl esters, dimethylcarbonate, and amides or amines, respectively. Adsorbed atomic oxygen plays an essential role in these reactions, ranging from being the active site for activation of alcohols and amines to a direct reactant in alkene oxidation.…”

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confidence: 99%

Tuning the Stability of Surface Intermediates Using Adsorbed Oxygen: Acetate on Au(111)

Cremer

Siler

Rodríguez‐Reyes

et al. 2014

J. Phys. Chem. Lett.

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Selective oxidative reactions promoted by gold depend critically on controlling the coverage and stability of adsorbed intermediates, as well as promoting specific bond activations of those intermediates. We demonstrate that acetate, a common intermediate in the oxidation of olefins, aldehydes, and alcohols, is destabilized by 7-10 kcal/mol by coadsorbed oxygen relative to its stability on the clean gold surface. The amount of destabilization depends on the oxygen coverage. Peak temperatures of products indicative of oxygen-assisted and clean-surface bond activation differ by up to 130 K. Experiments with d3-acetate show a kinetic isotope effect of 6.9 at 400 K, indicating that the rate-limiting step of the low temperature oxygen-assisted reaction is γ-CH bond breaking. This clearly demonstrates that coadsorbed oxygen activates γ-CH bonds on gold and suggests that an oxygen-assisted activation may also occur for β-CH bonds crucial in oxygen-assisted alcohol coupling on metallic gold catalysts, as predicted by theory.

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Highly Selective Acylation of Dimethylamine Mediated by Oxygen Atoms on Metallic Gold Surfaces

Cited by 24 publications

References 31 publications

Promotional effects of chemisorbed oxygen and hydroxide in the activation of C–H and O–H bonds over transition metal surfaces

Promotional effects of chemisorbed oxygen and hydroxide in the activation of C–H and O–H bonds over transition metal surfaces

Density functional theory in surface chemistry and catalysis

Tuning the Stability of Surface Intermediates Using Adsorbed Oxygen: Acetate on Au(111)

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