Assessing Combinations of B(C6 F5 )3 and N2 -Derived Molybdenum Nitrido Complexes for Heterolytic Bond Activation

Chemistry. 2023 May 8;29(26):e202203774. doi: 10.1002/chem.202203774. Epub 2023 Mar 24.

Abstract

Two different dinitrogen-derived molybdenum nitrido complexes varying by their geometry, ligand spheres and oxidations states were shown to engage their N ligand in dative bonding with the strong Lewis acid B(C6 F5 )3 . The stable adducts were assessed for frustrated Lewis pair-type heterolytic E-H bond splitting of hydrosilanes (E=Si) and HB(C6 F5 )2 . Whereas Si-H bond activation was achieved, HB(C6 F5 )2 was shown to substitute B(C6 F5 )3 in a quantitative or equilibrated fashion, depending on the nature of the nitrido complex. No B-H bond splitting was observed. Thermodynamics of these reactions, computed by DFT, are in agreement with the experimental outcomes.

Keywords: dinitrogen; frustrated Lewis pairs; molybdenum; nitrido complexes; silanes.