Tripodal trispyrazolylborates (Tp) are a well-known class of scorpionate ligands, widely used for the synthesis of complexes with interesting electronic and structural properties. Gratifyingly, 3,5-disubstitution of pyrazolyl arms on Tp ligand renders shielding for the bound metal, granting the formation of low-coordinate metals featuring metal-ligand multiple bonds, which are an interesting class of molecules both for their electronic properties and their reactivity. In the case of vanadium, vanadium nitrides are not only a likely intermediate in vanadium-based nitrogen fixation processes but also a potential catalyst for reduction/oxidation reactions. These promising materials also possess compelling electronic conductivity and high specific capacity. However, in contrast to the ubiquity of vanadyl ions (VO2+), there are very few examples of mononuclear neutral and anionic vanadium nitrides. Hence, we have pursued the synthesis of such metal-ligand multiply bound species using TptBu,Me. The VTptBu,MeCl and VTptBu,MeCl2 precursors have been studied electronically using X- and Q-band EPR, and HF-EPR respectively. Additionally, these complexes were characterized by a variety of methods, including single-crystal x-ray crystallography. In this talk, I will present the synthesis, characterization, and reactivity of several multiply bound terminal and bridging pnictides and chalcogenides. CV, EPR, and SQUID data have been also collected to provide a better electronic and magnetic understanding of such complexed molecules.

Vanadium pnictide and chalcogenide complexes supported by the scorpionate TptBu,Me ligand

ACS Spring Meeting 2021

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