Dataset Information

An Electron-Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces.

ABSTRACT: The structural properties and binding motif of a strongly ?-electron-donating N-heterocyclic carbene have been investigated on different transition-metal surfaces. The examined cyclic (alkyl)(amino)carbene (CAAC) was found to be mobile on surfaces, and molecular islands with short-range order could be found at high coverage. A combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations highlights how CAACs bind to the surface, which is of tremendous importance to gain an understanding of heterogeneous catalysts bearing CAACs as ligands.

SUBMITTER: Bakker A

PROVIDER: S-EPMC7496406 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

ACCESS DATA

Publications

An Electron-Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces.

Bakker Anne A Freitag Matthias M Kolodzeiski Elena E Bellotti Peter P Timmer Alexander A Ren Jindong J Schulze Lammers Bertram B Moock Daniel D Roesky Herbert W HW Mönig Harry H Amirjalayer Saeed S Fuchs Harald H Glorius Frank F

Angewandte Chemie (International ed. in English) 20200603 32

The structural properties and binding motif of a strongly σ-electron-donating N-heterocyclic carbene have been investigated on different transition-metal surfaces. The examined cyclic (alkyl)(amino)carbene (CAAC) was found to be mobile on surfaces, and molecular islands with short-range order could be found at high coverage. A combination of scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations highlights how CAACs bind to t ...[more]

PMID: 32267051

Similar Datasets

Project description:Accurately modeling heterogeneous catalysis requires accurate descriptions of rate-controlling elementary reactions of molecules on metal surfaces, but standard density functionals (DFs) are not accurate enough for this. The problem can be solved with the specific reaction parameter approach to density functional theory (SRP-DFT), but the transferability of SRP DFs among chemically related systems is limited. We combine the MS-PBEl, MS-B86bl, and MS-RPBEl semilocal made simple (MS) meta-generalized gradient approximation (GGA) (mGGA) DFs with rVV10 nonlocal correlation, and we evaluate their performance for the hydrogen (H2) + Cu(111), deuterium (D2) + Ag(111), H2 + Au(111), and D2 + Pt(111) gas-surface systems. The three MS mGGA DFs that have been combined with rVV10 nonlocal correlation were not fitted to reproduce particular experiments, nor has the b parameter present in rVV10 been reoptimized. Of the three DFs obtained the MS-PBEl-rVV10 DF yields an excellent description of van der Waals well geometries. The three original MS mGGA DFs gave a highly accurate description of the metals, which was comparable in quality to that obtained with the PBEsol DF. Here, we find that combining the three original MS mGGA DFs with rVV10 nonlocal correlation comes at the cost of a slightly less accurate description of the metal. However, the description of the metal obtained in this way is still better than the descriptions obtained with SRP DFs specifically optimized for individual systems. Using the Born-Oppenheimer static surface (BOSS) model, simulations of molecular beam dissociative chemisorption experiments yield chemical accuracy for the D2 + Ag(111) and D2 + Pt(111) systems. A comparison between calculated and measured E 1/2(ν, J) parameters describing associative desorption suggests chemical accuracy for the associative desorption of H2 from Au(111) as well. Our results suggest that ascending Jacob's ladder to the mGGA rung yields increasingly more accurate results for gas-surface reactions of H2 (D2) interacting with late transition metals.

Dataset Information

An Electron-Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces.

Publications

An Electron-Rich Cyclic (Alkyl)(Amino)Carbene on Au(111), Ag(111), and Cu(111) Surfaces.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets