Probing the microhydration of metal carbonyls: a photoelectron velocity-map imaging spectroscopic and theoretical study of Ni(CO) 3 (H 2 O) n

• Published in: Physical chemistry chemical physics : PCCP Vol. 18; no. 38; pp. 26719 - 26724
• Main Authors: Xie, Hua, Zou, Jinghan, Kong, Xiangtao, Zhang, Weiqing, Ahmed, Musahid, Jiang, Ling
• Format: Journal Article
• Language: English
• Published: England Royal Society of Chemistry 29.09.2016
• Subjects: Clusters; Imaging; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Nickel; Photoelectrons; Solvation; Spectroscopy; Terminals; Water chemistry
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/c6cp05035b

A series of microhydrated nickel carbonyls, Ni(CO) (H O) (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 for 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.