A simple apparatus for fiber-optic reflectance FTIR spectroelectrochemical measurements is described.. The method is useful for observing the products of electrode reactions generated in steady-state at an electrode surface, and the problem of large thin-layer resistance in non-aqueous solvents is minimized. Cyclic voltammetry (CV) and FTIR spectroelectrochemical measurements on five compounds ([(eta(5)-C5H5)Fe(CO)(2)](2) (Fp(2)), Fp(C=CPh), Mn-2(CO)(10), BrMn(CO)(5) and (eta(5)-2,4-diphenyl-6-methylpyranyl)tricarbonylmanganese (PyrMn(CO)(3)) are presented. As expected, Mn-2(CO)(10) and BrMn(CO)(5) are both reduced to the known Mn(CO)(5)(-) anion, but Fo(2) is reduced in CH2Cl2 to form FpCH(2)Cl, and Fp(C=CPh) forms a [mu(2)-eta(1):eta(2)-Fp(2)C=CPh](+) cation. Upon oxidation of the PyrMn(CO)(3) complex, the Mn(CO)(3)(+) unit undergoes migration from the pyranyl ring to a phenyl ring to form an eta(6)-ariene complex which has a pyrylium ion as a substituent on the arene ligand.