The structure and reactivity of intermediates in the photocatalytic cycle of a proton reduction catalyst, [Fe2(bdt)(CO)6] (bdt = benzenedithiolate), were investigated by time-resolved spectroscopy. The singly reduced catalyst [Fe2(bdt)(CO)6](-), a key intermediate in photocatalytic H2 formation, was generated by reaction with one-electron reductants in laser flash-quench experiments and could be observed spectroscopically on the nanoseconds to microseconds time scale. From UV/vis and IR spectroscopy, [Fe2(bdt)(CO)6](-) is readily distinguished from the two-electron reduced catalyst [Fe2(bdt)(CO)6](2-) that is obtained inevitably in the electrochemical reduction of [Fe2(bdt)(CO)6]. For the disproportionation rate constant of [Fe2(bdt)(CO)6](-), an upper limit on the order of 10(7) M(-1) s(-1) was estimated, which precludes a major role of [Fe2(bdt)(CO)6](2-) in photoinduced proton reduction cycles. Structurally [Fe2(bdt)(CO)6](-) is characterized by a rather asymmetrically distorted geometry with one broken Fe-S bond and six terminal CO ligands. Acids with pK(a) ≤ 12.7 protonate [Fe2(bdt)(CO)6](-) with bimolecular rate constants of 4 × 10(6), 7 × 10(6), and 2 × 10(8) M(-1) s(-1) (trichloroacetic, trifluoroacetic, and toluenesulfonic acids, respectively). The resulting hydride complex [Fe2(bdt)(CO)6H] is therefore likely to be an intermediate in photocatalytic cycles. This intermediate resembles structurally and electronically the parent complex [Fe2(bdt)(CO)6], with very similar carbonyl stretching frequencies.