Photochemical Reaction of Mo(CO)6 with Et2GeH2: NMR and DFT Studies of Reaction Products; Crystal Structure of a Novel Complex [{Mo(μ-η2-H-GeEt2)(CO)4}2]

The photochemical reaction of Mo(CO)(6) with the diethylgermane Et2GeH2 leads to the formation of several new complexes, which were detected by IR and H-1 and C-13 NMR spectroscopy. From the mixture of compounds, a binuclear complex, [{Mo(mu-eta(2)-H-GeEt2)(CO)(4)}(2)], was isolated in crystalline form, and its molecular structure was established by single-crystal X-ray diffraction studies. The agostic hydride ligand of the Mo(mu-eta(2)-H-GeEt2) group was located in the structure at a chemically reasonable position between the Mo and Ge atoms of the Mo-Ge bond of the bridging germyl ligand, and its presence was confirmed by H-1 NMR spectroscopy due to a proton resonance at delta = -7.86. Two dihydride complexes were identified by H-1 and C-13 NMR spectroscopy, due to their differing thermal behavior. A DFT study of the structural properties of possible reaction products was performed.