Treatment of [HB(3,5-(CF3)2Pz)3]Na(THF) with CF3SO3Cu followed by 1-azidoadamantane affords [HB(3,5-(CF3)2Pz)3]CuNNN(1-Ad) in 65% yield. The solid state structure shows that the copper atom is coordinated to the terminal nitrogen atom (NT) of the azidoadamantane ligand. The related silver(I) adduct can be prepared in 80% yield by the treatment of [HB(3,5-(CF3)2Pz)3]Ag(THF) with 1-azidoadamantane. However, [HB(3,5-(CF3)2Pz)3]AgN(1-Ad)NN shows a different bonding mode where the silver atom coordinates to the alkylated nitrogen atom (NA) of the azidoadamantane ligand. Asymmetric stretching bands of the azido group for copper and silver adducts appear at 2143 and 2120 cm-1, respectively. Theoretical investigation shows that steric effects do not play a dominant role in determining the bonding mode of the azide ligand in these two metal complexes. Although the copper(I) ion affinity for the two coordinating sites NT and NA is nearly identical, copper-azide back-bonding interactions favor the copper-NT mode of bonding over the copper-NA mode. Silver (a very poor back-bonding metal) prefers the NA site for coordination. The NA site has a significantly higher proton affinity and slightly higher sodium ion affinity. Important structural parameters for [HB(3,5-(CF3)2Pz)3]CuNNN(1-Ad) and [HB(3,5-(CF3)2Pz)3]AgN(1-Ad)NN are as follows: Cu-NT 1.861(3) A, NT-N 1.136(4) A, N-NA 1.219(4) A, NT-N-NA 173.1(3) degrees; Ag-NA 2.220(5) A, NT-N 1.143(12) A, N-NA 1.227(10) A, NT-N-NA 176.8(12) degrees. Overall, the azidoadamantane ligand does not undergo any significant changes upon coordination to Cu(I) or Ag(I) ions.