[(i-Pr2Ph)(2)nacnacCr](2)(mu-eta(2):eta(2)-N-2) (2) has been prepared and structurally characterized; it contains a bridging side-on bonded dinitrogen ligand with a N-N distance of 1.249(5) A. Reactions of this reactive Cr(I) synthon with various small molecules resulted in a series of unusual molecules and transformations; thus CO yielded the binuclear isocarbonyl [(i-Pr2Ph)(2)nacnacCr](2)(CO)(mu-eta(1):eta(1)-CO)(2), ethylene gave [(i-Pr2Ph)(2)nacnacCr](2)(mu-eta(2):eta(2)-C2H4), O-2 oxidatively added to produce (i-Pr2Ph)(2)nacnacCr(O)(2), and azobenzene afforded the product of NN bond cleavage [(i-Pr2Ph)(2)nacnacCr](2)(mu-NPh)(2). 2 can be prepared in good yield and affords a facile entry to low-coordinate Cr(I) coordination chemistry.