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Influence of a Metal Substrate on Small‐Molecule Activation Mediated by a Surface‐Adsorbed Complex
Author(s) -
Schlimm Alexander,
Stucke Nadja,
Flöser Benedikt M.,
Rusch Talina,
Krahmer Jan,
Näther Christian,
Strunskus Thomas,
Magnussen Olaf M.,
Tuczek Felix
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201800911
Subject(s) - molybdenum , substrate (aquarium) , ligand (biochemistry) , chemistry , adsorption , molecule , polarizability , transition metal , metal , carbon monoxide , photochemistry , raman spectroscopy , crystallography , catalysis , chemical physics , inorganic chemistry , organic chemistry , biochemistry , oceanography , receptor , physics , optics , geology
Abstract 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 PN 3 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.