The reaction of [Mtren)Cl-2]Cl(M=Co(III), Cr(III) with benzene-1,2-dithiol, H-2(bdt), and 3,6-bis(trimethylsilyl)benzene-1,2-dithiol, H-2(tmsdt), in a water/methanol mixture in the presence of potassium tert-butodixe produced green crystals of [Mtren)(bdt)](PF6)(1/2)(Cl)(1/2)H2O (1(PF6)(1/2)(Cl)(1/2)center dot H2O, M = Co; 2(PF6)(1/2)(Cl)(1/2)center dot H2O, M = Cr) and [Mtren)(trnsdt)](PF6)(1/2)(Cl)(1/2)center dot H2O (1a(PF6)(1/2)(Cl)(1/2)center dot H2O, M =Co; 2a(PF6)(1/2)(Cl)(1/2)center dot H2O, M =Cr), respectively, upon addition of KPF6. The structures of 1 (PF6)(1/2)(Cl)(1/2), H2O and 2(PF6)(1/2)(Cl)(1/2)center dot H2O have be. en determined by X-ray crystallography. Octahedral 1 and 1a are diamagnetic whereas 2 and 2a possess an S = 3/2 ground state. Cyclic voltammeryof 1a and 2a in CH2Cl2 solution established that both species undergo a reversible one-electron oxidation generating die stable deatioiLs [Co-III(tren)(tmsdt(center dot))(2+) (S=1/2) and (Cr-III(tren(tmsdt(center dot))(2+) (S = 1) where (tmsdt(center dot))(1-) represents the pi radical monoanion of oxidized (tmsdt)(2-). The electrochemical oxidations art ligand centered processes. These dications have been investigated by UV-vis and EPR spectroscopy and density functional calculations using the B3L P functional. The S,g-coordinated benzene-1,2-dithiolate(1-) radical has been identified and unambiguously characterized. Comparison with the corresponding o-benzosemiquinonate(1-) complexes shows that the S,S-coordinated benzene-1,2-dithiolate(1-) radical is a sulfur centered radical whereas its oxygen containing analogue carries similar to 65% of die spin density oil die six-membered ring.