Converting the abundant, but largely inert, dinitrogen (N2) into the N-containing products upon which society relies (including proteins, explosives, and fertilizers) is a vital synthetic target as the worldwide population, and therefore demand for such commodities, continues to grow. The development of energetically and atomically efficient methods of cleaving, functionalizing, and releasing N2 as other valuable N-containing products (a process known as fixation) is of the utmost importance to sustainably meet the global demand. Transition-metal-mediated examples of N2 coordination, activation, cleavage, and N-atom product release are an attractive and active field of study in developing N2 fixation cycle that operate under mild conditions and consume few resources. Herein, the effects of a sterically reduced pentamethylcyclopentadienyl, amidinate (CPAM) ligand framework around group 6 metal centers (M = Mo, W) are investigated as a means of lowering barriers to reaction

in order to complete a novel N2 fixation cycle. The design and implementation of this set of reactions are reported, including synthesis and characterization of new dinitrogen and dinitrogen-derived organometallic compounds, as are the groundbreaking thermally mediated N≡N cleavage from dinuclear M(II) (μ-N2) to M(V) (μ-N)2 dinuclear complexes, N atom functionalization via silylation to form terminal Mo(IV) trimethylsilyl imidos, and a controlled, “dry hydrolysis” with Me3SiCl and a readily available silanol or alcohol proton source (XOH) to releases hexamethyldisilazane (HN(SiMe3)2) and a silyl ether (XOSiMe3) while regenerating the M(IV) dichloride starting material. Reactivities within and modifications to this cycle are explored, including the introduction of innovative reagents, and the versatility of the CPAM system is demonstrated while making strides towards more targeted and sustainable means of synthetic N2 fixation.