Direct Observation of a Bent Carbonyl Ligand in a 19-Electron Transition Metal Complex

The photochemistry of [CpRu­(CO)₂]₂ in P­(OMe)₃/CH₂Cl₂ solution has been studied using picosecond time-resolved infrared (TRIR) spectroscopy. Photolysis at 400 nm leads to the formation of 17-electron CpRu­(CO)₂^• radicals, which react on the picosecond time scale to form 19-electron CpRu­(CO)₂P­(OMe)₃^• adducts. The TRIR spectra of this adduct display an unusually low CO stretching frequency for the antisymmetric CO stretching mode, suggesting that one carbonyl ligand adopts a bent configuration to avoid a 19-electron count at the metal center. This spectral assignment is supported by analogous experiments on [CpFe­(CO)₂]₂ in the same solvent, combined with DFT studies on the structures of the 19-electron adducts. The DFT results predict a bent CO ligand in CpRu­(CO)₂P­(OMe)₃^•, whereas approximately linear Fe–C–O bond angles are predicted for CpFe­(CO)₂P­(OMe)₃^•. The observation of a bent CO ligand in the 19-electron ruthenium adduct is a surprising result, and it provides new insight into the solution-phase behavior of 19-electron complexes. TRIR spectra were also collected for [CpRu­(CO)₂]₂ in neat CH₂Cl₂, and it is interesting to note that no singly bridged [CpRu­(CO)]₂(μ-CO) photoproduct was observed to form following 400- or 267-nm excitation, despite previous observations of this species on longer time scales