Dataset Information

Mechanistic Study of Copper-Catalyzed C-H Hydroxylation/C-S Coupling by ESI-HR MS and DFT Calculations.

ABSTRACT: The reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling was studied using electrospray ionization high resolution mass spectrometry (ESI-HR MS) and density functional theory calculations (DFT). Notably, a series of CuI and CuIII complexes were observed as key intermediates and identified using ESI-HR MS. Furthermore, a catalyst cycle involving proton abstraction/oxidative addition/reductive elimination was proposed. This study is important and valuable with respect to C-H functionalization.

SUBMITTER: Xu R

PROVIDER: S-EPMC6150210 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

Mechanistic Study of Copper-Catalyzed C-H Hydroxylation/C-S Coupling by ESI-HR MS and DFT Calculations.

Xu Runsheng R Cai Rongrong R Zhou Sixian S Zhou Zhuoda Z Li Beibei B Xu Dihui D

Molecules (Basel, Switzerland) 20171106 11

The reaction mechanism of Cu-catalyzed C-H hydroxylation/C-S coupling was studied using electrospray ionization high resolution mass spectrometry (ESI-HR MS) and density functional theory calculations (DFT). Notably, a series of Cu<sup>I</sup> and Cu<sup>III</sup> complexes were observed as key intermediates and identified using ESI-HR MS. Furthermore, a catalyst cycle involving proton abstraction/oxidative addition/reductive elimination was proposed. This study is important and valuable with re ...[more]

PMID: 29113130

Similar Datasets

Project description:Layered materials, such as MoS2, are being intensely studied due to their interesting properties and wide variety of potential applications. These materials are also interesting as supports for low-dimensional metals for catalysis, while recent work has shown increased interest in using 2D materials in the electronics industry as a Cu diffusion barrier in semiconductor device interconnects. The interaction between different metal structures and MoS2 monolayers is therefore of significant importance and first-principles simulations can probe aspects of this interaction not easily accessible to experiment. Previous theoretical studies have focused particularly on the adsorption of a range of metallic elements, including first-row transition metals, as well as Ag and Au. However, most studies have examined single-atom adsorption or adsorbed nanoparticles of noble metals. This means there is a knowledge gap in terms of thin film nucleation on 2D materials. To begin addressing this issue, we present in this paper a first-principles density functional theory (DFT) study of the adsorption of small Cu n (n = 1-4) structures on 2D MoS2 as a model system. We find on a perfect MoS2 monolayer that a single Cu atom prefers an adsorption site above the Mo atom. With increasing nanocluster size the nanocluster binds more strongly when Cu atoms adsorb atop the S atoms. Stability is driven by the number of Cu-Cu interactions and the distance between adsorption sites, with no obvious preference towards 2D or 3D structures. The introduction of a single S vacancy in the monolayer enhances the copper binding energy, although some Cu n nanoclusters are actually unstable. The effect of the vacancy is localised around the vacancy site. Finally, on both the pristine and the defective MoS2 monolayer, the density-of-states analysis shows that the adsorption of Cu introduces new electronic states as a result of partial Cu oxidation, but the metallic character of Cu nanoclusters is preserved.

Dataset Information

Mechanistic Study of Copper-Catalyzed C-H Hydroxylation/C-S Coupling by ESI-HR MS and DFT Calculations.

Publications

Mechanistic Study of Copper-Catalyzed C-H Hydroxylation/C-S Coupling by ESI-HR MS and DFT Calculations.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure