The reaction of Ni(COD)(2) with two equivalents of the TEMPO radical at 68 degrees C affords the 16 e(-) "bowtie" complex Ni(eta(2)-TEMPO)(2), 1, in 78% yield. Compound 1 reacts with tert-butyl isocyanide and phenylacetylene at room temperature to yield the 16 e(-) distorted square planar nickel complexes Ni(eta(2)-TEMPO)(eta(1)-TEMPO)((CNBu)-Bu-t), 2, and Ni(eta(2)-TEMPO)(eta(1)-TEMPOH)(CCPh), 4, respectively. The facile reactivity of 1 is aided by the transition of the TEMPO ligand from an eta(2) to eta(1) binding mode. Complex 4 is an unusual example of hydrogen atom transfer from phenylacetylene to a coordinated TEMPO ligand.