The synthesis, structural characterization, and electrochemical properties of N3S2-ligated metal complexes of the ligand 4,10-dithia-1,7,13-triazabicyclo[11.3.3] are described. Complexes of Ni-II, Co-II, and Rh-III have been characterized by X-ray crystallography as six-coordinate complexes of the pentadentate ligand with Cl-anions occupying the position trans to the secondary amine donor. In addition, the chelation of the N3S2 donor ligand to the reactor-produced radionuclide Rh-105 was shown to give a single product in high yield (>98% at pH 5). The ligand is prepared by the template reaction of (N,N-bis(2-mercaptoethyl)-1,5-diazacyclooctane)nickel(II), Ni-1, with bis(2-chloroethyl)amine, yielding (S,S’-(3-aza-1,5 -pentanediyl)-N,N’-bis(2-mercaptoethyl)-1,5-diazacyclooctane N,N’,N",S,S’)nickel(II) chloride, [Ni(amine)Cl]Cl. Removal of nickel from [Ni(amine)Cl]Cl and subsequent reaction of the ligand with CoCl2 or RhCl3.xH(2)O afforded (S,S’-(3-aza-1,5-pentanediyl)-N,N’-bis(2-diazacyclooctane-N,N’N",S,S)cobalt(II) chloride, [Co(amine)Cl]Cl, C14H29N3S2CoCl2.1.75MeOH, and (S,S’-(3-aza-1 ,5-pentanediyl)-N,N’-bis (2-mercaptoethyl)-1,5-diazacyclooctane-N,N’,N",S,S’)rhodium(III) chloride, [Rh(amine)Cl]Cl-2, C14H29N3S2RhCl3, respectively. The blue complex [Ni(amine)Cl]Cl, C14H29N3S2NiCl2.MeOH, contains nickel in an octahedral environment of N3S2Cl donors and crystallizes in the monoclinic space group P2(1)/c with a = 13.278(3) Angstrom, b = 11.976(4) Angstrom, c = 12.928(4) Angstrom, beta = 102.17(2)degrees, and Z = 4. The complex [Co(amine)Cl]Cl is fuchsia and crystallizes in the monoclinic space group P2(1)/n with a = 10.321(2) Angstrom, b = 7.892(1) Angstrom, c = 27.684(3) Angstrom, beta = 96.91(1)degrees, and Z = 4. Yellow crystals of [Rh(amine)Cl]Cl-2, C14H29N3S2RhCl3, were determined to be in the monoclinic space group Clcl with a = 9.655(2) Angstrom, b = 16.805(4) Angstrom, c = 11.756(3) Angstrom, beta = 96.29(2)degrees, and Z = 4.