The bifunctional ligand catechol-4,5 dithiol, H(2)Dtcat, has been synthesized, and the structure of the bis Br- adduct, (HS)(2)C6H2(OH)(2)center dot 2Ph(4)Br center dot H2O, has been determined. The syntheses, molecular structures, electronic structures, and magnetic properties of the monoanionic [(Dtcat(2-))(2)M](-), (M = Ni, V and M = Cu, VI) complexes have been obtained as Ph4PBr double salts, [M(S2C6H2(OH)(2))(2)][Ph4P](3)Br-2. These and the antiferromagnetically coupled dimeric [(Dtcat)(2) Fe][Ph4P](2)center dot 4DMF complex, VII, have been structurally characterized. The centrosymmetric [M(S2C6H2(OH)(2))(2)](-) complexes in the X-ray isomorphous V and VI are connected via H-bonding to Br- ions to form one-dimensional chains well separated from each other by the Ph4P+ cations. Magnetic measurements show V to be a S = 1/2 and VI a S = O molecules. The distribution of electrons in these compounds have been determined by density functional theory calculations which show V to be a radical anion Ni(II) complex and VI a partially oxidized-ligand, reduced-copper complex. The 4,5 dithio-o-quinone [(Dtoq)(2)Ni][Ph4P](2) and [(Dtoq)(2)Cu][Ph4P](2) orthoquinone derivatives of V and VI have been obtained by oxidation, and their molecular structures have been determined. The dimeric {[FeS2C6H2(OH)(2)](2)}(2-) complex, (VII) also crystallizes in chains where all OH groups participate in extensive H-bonding. The structure of the dianion VII contains S-coordinated Fe(III) ions in a square pyramidal coordination. In VII, two low spin Fe(III) (S = 1/2) sites are weakly coupled antiferromagnetically with a mu(eff) of 2.81 BM at 270 K and 0.91 BM at 10 K.