Photoreaction of CpFe(CO)(2)Me with sterically congested R2GeH2 [R = 2,4,6-(C6H2Pr3)-Pr-i (Tip), 2,4,6-C6H2Me3 (Mes)] afforded paramagnetic germylene-bridged diiron complexes having a triplet ground state, Cp2Fe2(mu-CO)(2)(mu-GeR2) (3a, R = Tip; 3b, R = Mes), while the analogous reaction with R2SnH2 afforded diamagnetic complexes Cp2Fe2(CO)(2)(mu-CO)(mu-SnR2) (trans-5a, R = Tip; trans-5b, R = Mes). The structure of 3a was determined by X-ray crystallography.