Anion Photoelectron Imaging and Theoretical Study of Cu(CO)3-
Photoelectron velocity map images of Cu(CO)3-have been experimentally recorded in the 700-1100 nm range.The infrared-inactive Cu-C symmetric stretching modes for Cu(CO)3(v2 ≈367 cm-1)and Cu(CO)3-(v2≈ 408 cm-1),as well as the electron affinity(1.03±0.01 eV)of Cu(CO)3,are accurately determined from high resolution photoelectron spectra.In combination with quantum chemical calculations and bonding analyses,the coordination bonds in both Cu(CO)3-and Cu(CO)3 are found to be due to back-donation π bonding type,formed via electron promotion from Cu's 4s orbital to the 4p orbital,which is consequently donated to the unoccupied anti-bonding π*orbitals of the car-bonyl groups.The attachment of an additional electron to Cu(CO)3 strengthens the Cu-CO coordination,making Cu(CO)3-more stable.The intramolecular interactions between the Cu/Cu-and carbonyl groups are found to be primarily governed by electrostatic forces and orbital interactions.
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