Electronic spectroscopic and electrochemical data are presented for RU(P(C18H37)(3))(2)(DTBSq)(2) (DTBSq = 3,5-di-tert-butyl-o-benzosemiquinonate). The compound contains "non-innocent" dioxolene ligands (dioxolene refers to any of the series catechol-semiquinone-quinone), which show rich electrochemical and spectroscopic properties. The long alkyl chains attached to the phosphine ligands permit the casting of organized Langmuir-Blodgett (LB) films which were electrochemically characterized as the free standing film in-situ in the Langmuir-Blodgett trough. One reversible film oxidation wave was observed with an indium doped tin oxide electrode touching (horizontally) the floating Langmuir-Blodgett film on the subphase surface. Interactions between the electroactive monolayers and redox species in the subphase are probed using cyclic voltammetry. Evidence is presented for direct interaction of the surface film and subphase species.