Irradiation of 1a and 0.5 equiv. of [Fe(η 5 -C5H5)(CO)2]2 for 6 hours with either a 390 or 428 nm LED lamp (40 W) leads to the formation of a mixture of heterometallic species 2a and 3a in a 1:1 ratio (Scheme 1a). The mixture of 2a and 3a in benzene-d6 showed no changes over time at 25 °C, or upon heating to 100 °C. Both 2a and 3a are diamagnetic and can be assigned formal oxidation states of Fe(0) and Fe(II) respectively. Complex 2a is a Zn-Fe adduct which has been previously reported by Mankad and co-workers, while complex 3a features two bridging hydride groups linking the Zn and Fe centres. Formation in a 1:1 ratio conserves the reaction stoichiometry. Generation of 3a could be considered to derive from: (i) 1a reacting with [Fe(η 5 -C5H5)(CO)2]2 to form 2a and [Fe(η 5 -C5H5)(H)(CO)2] 21-23 as a transient intermediate which is then trapped by a second equiv. of 1a to form 3a or (ii) addition of in situ generated H2 across the Zn-Fe bond of 2a under photochemical conditions. To test this second potential mechanism involving photochemical H2 splitting, 1a and [Fe(η 5 -C5H5)(CO)2]2 were reacted with dihydrogen (1 bar) under LED light. A change in the ratio of the two products was observed reaching a 0.2:0.8 (2a:3a) mixture in 6 hours (Scheme 1a).