Transition metal complexes form the basis for small molecule activation and are relevant for electrocatalysis. To combine both approaches the attachment of homogeneous catalysts to metallic surfaces is of significant interest. Towards this goal a molybdenum tricarbonyl complex supported by a tripodal phosphine ligand was covalently bound to a triazatriangulene (TATA) platform via an acetylene unit and the resulting TATA-functionalised complex was deposited on a Au(111) surface. The corresponding self-assembled monolayer was characterised with scanning tunnelling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and near-edge X-ray absorption fine structure (NEXAFS). The vibrational properties of the surface-adsorbed complexes were investigated with the help of infrared reflection absorption spectroscopy (IRRAS), and the frequency/intensity changes with respect to the bulk spectrum were analysed. A full vibrational analysis was performed with the help of DFT.
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http://dx.doi.org/10.1039/d0dt03549a | DOI Listing |
Rev Sci Instrum
November 2024
Institute for Inorganic Chemistry, Christian-Albrechts-Universität zu Kiel, Max-Eyth-Straße 2, 24118 Kiel, Germany.
Dalton Trans
November 2024
Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel, Max-Eyth-Straße 2, 24118 Kiel, Germany.
Chemistry
April 2024
Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel, Max-Eyth Straße 2, 24118, Kiel, Germany.
Adsorption of metal-organic complexes on metallic surfaces to produce well-defined single site catalysts is a novel approach combining the advantages of homogeneous and heterogeneous catalysis. To avoid the "surface trans-effect" a dome-shaped molybdenum(0) tricarbonyl complex supported by an tolylazacalix[3](2,6)pyridine ligand is synthesized. This vacuum-evaporable complex both activates CO and reacts with molecular oxygen (O) to form a Mo(VI) trioxo complex which in turn is capable of catalytically mediating oxygen transfer.
View Article and Find Full Text PDFChemistry
April 2024
Institute of Inorganic Chemistry, Christian-Albrechts-University of Kiel, Max-Eyth Straße 2, 24118, Kiel, Germany.
The conversion of an azacalixpyridine-supported Mo(0) tricarbonyl into a Mo(VI) trioxo complex with dioxygen (O) is investigated in homogeneous solution and in a molecular film adsorbed on Au(111) using a variety of spectroscopic and analytical methods. These studies in particular show that the dome-shaped carbonyl complex adsorbed on the metal surface has the ability to bind and activate gaseous oxygen, overcoming the so-called surface trans-effect. Furthermore, the rate of the conversion dramatically increases by irradiation with light.
View Article and Find Full Text PDFACS Biomater Sci Eng
April 2023
CICECO - Aveiro Institute of Materials, Department of Chemistry, University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal.
Metal-organic frameworks (MOFs) have high potential as nanoplatforms for the storage and delivery of therapeutic gasotransmitters or gas-releasing molecules. The aim of the present study was to open an investigation into the viability of tricarbonyl-pyrazine-molybdenum(0) MOFs as carbon monoxide-releasing materials (CORMAs). A previous investigation found that the reaction of Mo(CO) with excess pyrazine (pyz) in a sealed ampoule gave a mixture comprising a major triclinic phase with pyz-occupied hexagonal channels, formulated as -Mo(CO)(pyz)·1/2pyz (), and a minor dense cubic phase, formulated as -Mo(CO)(pyz) ().
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