Lawrence Berkeley National Laboratory
Probing the microhydration of metal carbonyls: A photoelectron velocity-map imaging spectroscopic and theoretical study of Ni(CO)3(H2O): N-
- Author(s): Xie, H
- Zou, J
- Kong, X
- Zhang, W
- Ahmed, M
- Jiang, L
- et al.
Published Web Locationhttps://doi.org/10.1039/c6cp05035b
© 2016 the Owner Societies. A series of microhydrated nickel carbonyls, Ni(CO)3(H2O)n-(n = 0-4), are prepared via a laser vaporization supersonic cluster source in the gas phase and identified by mass-selected photoelectron velocity-map imaging spectroscopy and quantum chemical calculations. Vertical detachment energies for the n = 1-4 anions are measured from the photoelectron spectra to be 1.429 ± 0.103, 1.698 ± 0.090, 1.887 ± 0.080, and 2.023 ± 0.074 eV, respectively. The C-O stretching vibrational frequencies in the corresponding neutral clusters are determined to be 1968, 1950, 1945, and 1940 cm-1for n = 1-4, respectively, which are characteristic of terminal CO. It is determined that the hydrogen atom of the first water molecule is bound to the nickel center. Addition of a second water molecule prefers solvation at the carbonyl terminal. Spectroscopy combined with theory suggests that the solvation of nickel tricarbonyl is dominated by a water-ring network. The present findings would have important implications for the fundamental understanding of the multifaceted mechanisms of the multibody interaction of water and carbon monoxide with transition metals.