No abstract

In this work, we investigated how the reductive activation of CO with an atomic bismuth model catalyst changes under aprotic solvation. IR photodissociation spectroscopy of mass-selected [Bi(CO ) ] cluster ions was used to follow the structural evolution of the core ion with increasing cluster size. We interpreted the IR spectra by comparison with density-functional-theory calculations. The results show that CO binds to a bismuth atom in the presence of an excess electron to form a metalloformate ion, BiCOO . Solvation with additional CO molecules leads to the stabilization of a bismuth(I) oxalate complex and results in a core ion switch.

We report infrared photodissociation spectra of manganese-CO cluster anions, [Mn(CO)] (n = 2-10) to probe structural motifs characterizing the interaction between Mn and CO in the presence of an excess electron. We interpret the experimental spectra through comparison with infrared spectra predicted from density functional theory calculations. The cluster anions consist of core ions combining a Mn atom with a variety of ligands, solvated by additional CO molecules. Structural motifs of ligands evolve with increasing cluster size from simple monodentate and bidentate CO ligands to oxalate ligands and combinations of these structural themes.

Sup 13.3μm is exp 100fs pulses a