The tetracarbonyl compounds [W(mdt)(CO)(4)] (1) and [W(Me(2)pipdt)(CO)(4)] (2) both have dithiolene-type ligands (mdt(2-) = 1,2-dimethy1-1,2-dithiolate; Me(2)pipdt = 1,4-dimethylpiperazine-2,3-dithione) but different geometries, trigonal prismatic (TP) and octahedral, respectively. Structural data suggest an ene-1,2-dithiolate ligand description, hence a divalent tungsten ion, for 1 and a dithioketone ligand, hence W(0) oxidation state, for 2. Density functional theory (DFT) calculations on 1 show the highest occupied molecular orbital (HOMO) to be a strong W-dithiolene pi bonding interaction and the lowest unoccupied molecular orbital (LUMO) its antibonding counterpart. The TP geometry is preferred because symmetry allowed mixing of these orbitals via a configuration interaction (CI) stabilizes this geometry over an octahedron. The TP geometry for 2 is disfavored because W-dithiolene pi overlap is attenuated because of a lowering of the sulfur content and a raising of the energy of this ligand pi orbital by the conjugated piperazine nitrogen atoms in the Me(2)pipdt ligand. A survey of the Cambridge Structural Database identifies other W(CO)(4) compounds with pseudo C-4v disposition of CO ligands and suggests a d(4) electron count to be a probable common denominator. Reduction of 1 induces a geometry change to octahedral because the singly occupied molecular orbital (SOMO) is at lower energy in this geometry. The cyclic voltammogram of 1 in CH2Cl2 reveals a reduction wave at -1.14 V (vs Fc(+)/Fc) with an unusual offset between the cathodic and the anodic peaks (Delta E-p) of 0.130 V, which is followed by a second, reversible reduction wave at -1.36 V with Delta E-p = 0.091 V. The larger Delta E-p observed for the first reduction is evidence of the trigonal prism-to-octahedron geometry change attending this process. Tungsten L-1-edge X-ray absorption (XAS) data indicate a higher metal oxidation state in 1 than 2. Electron paramagnetic resonance data for [1](-) and [2](-) are both diagnostic of dithiolene ligand-based sulfur radical, indicating that one-electron reduction of 1 involves two-electron reduction of tungsten and one-electron oxidation of dithiolene ligand.