Beta-elimination is explored as a possible means of nitrogen-atom transfer into organic molecules. Molybdenum(IV) ketimide complexes of formula (Ar[t-Bu]N)(3)Mo(N=C(X)Ph), where Ar=3,5-Me2C6H3 and X=SC6F5, SeC6F5, or O2CPh, are formally derived from addition of the carbene fragment [:C(X)Ph] to the terminal nitrido molybdenum(VI) complex (Ar[t-Bu]N)(3)MO=-N in which the nitrido nitrogen atom is installed by scission of molecular nitrogen. Herein the pivotal (Ar[t-Bu]N)(3)Mo(N=C(X)Ph) complexes are obtained through independent synthesis, and their propensity to undergo beta-X elimination, i.e., conversion to (Ar[t-Bu]N)(3)MOX+PhC equivalent to N, is investigated. Radical C-X bond formation reactions ensue when benzonitrile is complexed to the three-coordinate molybdenum(III) complex (Ar[t-Bu]N)(3)Mo and then treated with 0.5 equiv of X-2, leading to facile assembly of the key (Ar[t-Bu]N)(3)Mo(N=C(X)Ph) molecules. Treated herein are synthetic, structural, thermochemical, and kinetic aspects of (i) the radical C-X bond formation and (ii) the ensuing beta-X elimination processes. Beta-X elimination is found to be especially facile for X=O-2-CPh, and the reaction represents an attractive component of an overall synthetic cycle for incorporation of dinitrogen-derived nitrogen atoms into organic nitrile (R-C equivalent to N) molecules.