Reduction of Tc(NAr’)(3)I (Ar’ = 2,6-dimethylphenyl) by 1 equiv of sodium generates the edge-bridged tetrahedral dimer complex TC2(NAr’)(4)(mu-NAr’)(2). In contrast, reduction of the more sterically hindered Tc(NAr)(3)I (Ar = 2,6-diisopropylphenyl) by 1 equiv of elemental sodium yields the "ethane-like" dimer Tc-2(NAr)(6), which can be further reduced with another equivalent of sodium (per technetium) to produce Tc(NAr)(3)(-). Tc(NAr)(3)(-) reacts with sources of metal cations such as HgBr2 and ClAu(PPh(3)) to form (ArN)(3)TcHgBr, (ArN)(3)TcHgTc(NAr)(3), and (ArN)(3)TcAu(PPh(3)). Tc(NAr)(3)(-) also reacts with MeI to form Tc(NAr)(3)Me and with Tc(NAr)(3)I to form the "ethane-like" dimer Tc-2(NAr)(6). X-ray structural characterization of the ethane-like Tc-2(NAr)(6) reveals unbridged Tc-Tc and Tc-N distances of 2.744(1) and 1.758(2) Angstrom, respectively. X-ray characterization of the tetrahedral edge-bridged Tc-2(NAr’)(6) reveals averaged Tc-Tc, Tc-N, and Tc-mu-N distances of 2.681(2), 1.750(8), and 1.954(7) Angstrom, respectively. X-ray analysis of (ArN)(3)TcAuPPh(3) reveals Tc-Au, Tc=N, and Au-P distances of 2.589(1), 1,758(5), and 2.278(2) Angstrom, respectively. Tc-Au-P, Au-Tc-N, and N-Tc-N angles are 180.0(1), 97.2(1), and 118.4(1)degrees. X-ray analysis of [Tc(NAr)(3)]Hg-2 gives Tc-Hg and Tc-N distances of 2.615(1) and 1.718(10) Angstrom and Tc-Hg-Tc, Hg-Tc-N, and N-Tc-N angles of 180.0(1), 97.6(4), and 118.3(2)degrees. Fenske-Hall molecular orbital calculations have been used to probe the electronic structure and bonding of tetrahedral edge-bridged and staggered ethane-like dimeric isomers of d(1)-d(1) Tc-2(NH)(6). A "frozen pi-orbital" method was utilized to separate sigma- and pi-bonding effects of the imido ligand to the dinuclear metal centers. Crystals of Tc-2(NAr’)(4)(mu-NAr’)(2) are monoclinic (P2(1)/n) with a = 19.500(8) Angstrom, b = 10.497(6) Angstrom, c = 22.684(8) Angstrom, beta = 110.37(3)degrees, V = 4353 Angstrom(3), rho(calc) = 1.39 g.cm(-3), and Z = 4. Crystals of (ArN)(3)TcHgTc(NAr)(3) are cubic (Pa (3) over bar) with a = 19.560(3) Angstrom, V= 7484 Angstrom(3), rho(calc) = 1.29 g.cm(-3), and Z = 8. Crystals of (ArN)(3)TcAu(PPh(3)) are rhombohedral (R (3) over bar) with a = 14.943(3) Angstrom, c 39.607(12) Angstrom, V = 7657 Angstrom(3), rho(calc) = 1.41 g.cm(-3), and Z = 6.