Nitrogen-Atom Exchange Mediated by Nitrido Complexes of Molybdenum Robyn L. Gdula Marc J. A. Johnson Nathan W. Ockwig 10.1021/ic051859q.s002 https://acs.figshare.com/articles/dataset/Nitrogen_Atom_Exchange_Mediated_by_Nitrido_Complexes_of_Molybdenum/3252475 Nitrido complexes N⋮Mo(OC(CF<sub>3</sub>)<sub>2</sub>Me)<sub>3</sub> (<b>1</b>) and N⋮Mo(OC(CF<sub>3</sub>)<sub>3</sub>)<sub>3</sub>(NCMe) (<b>2</b>) containing fluorinated alkoxide ancillary ligands are synthesized in 57% and 50% yield, respectively. Both complexes undergo N-atom exchange within hours at 30 °C with acetonitrile and benzonitrile in either THF-<i>d</i><sub>8</sub> or CD<sub>2</sub>Cl<sub>2</sub>, as shown by <sup>15</sup>N NMR studies using labeled <sup>15</sup>NCMe. In both solvents, <b>2</b> is the more active in this process. Additionally, both compounds are substantially more active in THF-<i>d</i><sub>8</sub> than in CD<sub>2</sub>Cl<sub>2</sub>. Complex <b>2</b> crystallizes in the space group <i>P</i>2(1)/<i>c</i>, adopting a pseudo-square-pyramidal structure in which the nitrido moiety occupies the apical position, 1.633(3) Å away from Mo. 2005-12-12 00:00:00 apical position compound 15 NCMe Mediated alkoxide nitrido moiety ligand complex acetonitrile benzonitrile solvent Molybdenum Nitrido Complexes THF 15 N NMR studies CD 2 Cl 2 Mo Complex 2 crystallizes