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High-valent metal oxo species stabilized by polyoxovanadates: synthesis, properties and catalytic activity

Subject Area Inorganic Molecular Chemistry - Synthesis and Characterisation
Term from 2017 to 2023
Project identifier Deutsche Forschungsgemeinschaft (DFG) - Project number 389183496
 
Final Report Year 2023

Final Report Abstract

Highly valent metal-oxo species are considered as key intermediates in a wide variety of industrial and biological catalysts. The present research project investigates the formation, reactivity and possible stabilization of highly valent metal-oxo and metal-hydroxo species on newly developed molecular vanadium oxides. Metal-functionalized vanadium oxide clusters [M(L)V12O32X]n- (= {MV12}, M = transition metal, L = terminal ligand, X = halide template), to which redox-active metal centers can be bound in a well-defined oxo-bonding pocket and whose oxidation catalytic activity has been demonstrated in preliminary work, serve as model systems. This project considers in particular multi-oxidizable metals of the 3d group (FeII, MnII, CoII) and lewis acidic centers (Ca2+, Mg2+, Ln3+, etc.) as molecular oxidation catalysts as well as possible models for industrial catalysts (e.g. Haber-Bosch catalysts) as well as for enzymes (e.g. dioxygenase). The binding situation of the metals in {MV12} differs fundamentally from classical metal-oxo ligands (often: nitrogen donors in trigonal coordination geometry), accordingly novel intermediates are expected in a so far hardly investigated binding situation with correspondingly unknown reactivity. In the first step, the formation of highly valent species by reaction of already available {MV12} complexes with reactive ligands such as peroxides as well as the possible activation of molecular oxygen on previously reduced {MV12} species will be investigated for this purpose. Highly valent intermediates are characterized by experimental and theoretical methods to gain insight into their electronic structure, bonding ratios, and reactivity. Structural studies on crystalline samples will provide detailed insight into the binding situation when possible. The reactivity of the generated species as well as their potential catalytic use will be investigated using synthetically important substrate oxidations such as C-H activations. In situ stability studies will provide information on possible rearrangements or colloid formation. The project thus opens access to a completely novel class of compounds whose reactivity can be rationalized by understanding the intermediates that occur and controlled at the molecular level by choosing the appropriate metal centers.

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