Wavelength-dependent photofragmentation and photoionization of gaseous (eta4-cycloocta-1,5-diene)(eta5-cyclopentadienyl)cobalt.

Abstract

Gas-phase photoreactions and photoproducts of the mixed-ligand compound (eta(4)-cycloocta-1,5-diene)(eta(5)-cyclopentadienyl)cobalt are reported. Significant amounts of the monoligated complexes CoCOD and CoCp are produced, and the relative amounts are wavelength dependent. The COD ligand (with the weakest metal-ligand bonds) is always preferentially labilized as expected, but the relative amounts of the CoCOD and CoCp fragments change by 1 order of magnitude as the excitation wavelength is changed. The gas-phase photoreactions exhibit other surprising features that are uncommon in the photoreactions of organometallic compounds in the gas phase. Significant amounts of the intact cation are formed, in contrast to most reported reactions where fragmentation of the weak metal-ligand bonds precedes ionization. Most surprisingly, fragmentation of the ligands occurs while the ligands are still coordinated. The resulting metal complexes contain ligand fragments that remain coordinated to the metal. Breaking several carbon-carbon bonds with retention of weaker metal-ligand bonds is unexpected. For example, C(5)H(5) undergoes fragmentation while still coordinated to the cobalt, yielding smaller compounds such as Co(CH)(+), Co(C(2)H(2))(+), Co(C(3)H(3))(+), and Co(C(4)H(6))(+). Correspondingly, coordinated COD yields Co(C(6)H(6))(+), Co(C(5)H(5))(+), Co(C(4)H(6))(+), Co(C(3)H(3))(+), Co(C(2)H(2))(+), and Co(CH)(+). The wavelength dependence of the ligand labilization is examined by utilizing mass-selected resonance enhanced multiphoton ionization spectroscopy. Both broad bands and sharp lines are observed in the mass-selected excitation spectra. The action spectra obtained in the gas phase while monitoring the cobalt ion follow the absorption onset found in solution. The changes in fragmentation pathways are interpreted in terms of the initially accessed excited state.