The ore-bridged technetium(III) polypyridyl complex, [(tpy)(Me(2)bpy)Tc-O-Tc(tpy)(Me(2)bpy)](OTf)(4) 1, abbreviated [(N5Tc)(2)O](4+), was prepared from the reaction of TcCl3(tpy), TlOTf, and adventitous water. In contrast to other known mu-oxo systems of technetium or ruthenium, the cyclic voltammetric data of [(N5Tc)(2)O](4+) suggests a relatively weak metal-metal interaction, however the visible absorption spectrum and the apparent magnetic properties suggests that this interaction cannot be completely dismissed. Crystallographic data of 1 : triclinic, , a 12.906(2) Angstrom, b = 14.320(4) Angstrom, c = 19.568(2) Angstrom, alpha = 77.55(1)degrees, beta = 72.13(1)degrees, gamma = 76.83(2)degrees, V = 3308 Angstrom(3), Z = 2. The Tc-O bond lengths are 1.833(6) and 1.830(6) Angstrom, and the Tc-O-Tc bond angle is 171.1(3)degrees. The zinc reduction of 1 results in the two electron reduced ore-bridged dimer, [(N5Tc)(2)O](2+). Both complexes exhibit intense, low energy bands in the visible region characteristic of mu-oxo compounds, and these bands are red shifted by approximately 5000 cm(-1) in the reduced complex.