The photochemical reaction of M(CO)6(M=W, Mo) with diethyl silanes and germanes H2EEt2 (E=Si, Ge) leads to the formation of a mixture of hydride complexes of varying stability, which were observed mainly by 1H NMR spectroscopy. From the mixture of compounds, only the binuclear complexes of the type [{M(µ-η2-H-EEt2)(CO)4}2] were stable enough to isolate in crystalline from, and their molecular structure was established by single-crystal X-ray diffraction studies. The chemical shift of the bridging hydride ligand in the latter complexes was observed at –8.33 ppm (Mo-Si), -7.86 ppm (Mo-Ge), -9.31 ppm (W-Si) and -9.02 ppm (W-Ge).