Influence of a Metal Substrate on Small-Molecule Activation Mediated by a Surface-Adsorbed Complex.
Alexander SchlimmNadja StuckeBenedikt M FlöserTalina RuschJan KrahmerChristian NätherThomas StrunskusOlaf M MagnussenFelix TuczekPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2018)
Activating small molecules with transition metal complexes adsorbed on metal surfaces is a novel approach combining aspects of homogeneous and heterogeneous catalysis. In order to study the influence of an Au(111) substrate on the activation of the small-molecule ligand carbon monoxide, a molybdenum tricarbonyl complex containing a PN3 P pincer ligand was synthesized and investigated in the bulk, in solution, and adsorbed on an Au(111) surface. By means of a platform approach, a perpendicular orientation of the molybdenum complex was achieved and confirmed by IRRAS and NEXAFS. By using vibrational spectroscopy (IR, Raman, IRRAS) coupled to DFT calculations, the influence of the metal substrate on the activation of the CO ligands bound to the molybdenum complex was determined. The electron-withdrawing behavior of gold causes an overall shift of the CO stretching vibrations to higher frequencies, which is partly compensated by dynamic charge transfer from the substrate to the molybdenum center, which increases its (dynamic) polarizability.
Keyphrases
- small molecule
- density functional theory
- transition metal
- protein protein
- molecular dynamics simulations
- sensitive detection
- structural basis
- signaling pathway
- cystic fibrosis
- high throughput
- escherichia coli
- molecular docking
- amino acid
- staphylococcus aureus
- pseudomonas aeruginosa
- mass spectrometry
- single molecule
- biofilm formation
- single cell
- raman spectroscopy
- crystal structure
- solar cells