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Title: Probing the microhydration of metal carbonyls: a photoelectron velocity-map imaging spectroscopic and theoretical study of Ni(CO)3(H2O)n–

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/c6cp05035b· OSTI ID:1464132
 [1];  [1];  [1];  [1];  [2];  [1]
  1. Chinese Academy of Sciences, Dalian (People's Republic of China)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
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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–1 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. Here, 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.

Research Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1464132
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Vol. 18, Issue 38; Related Information: © 2016 the Owner Societies.; ISSN 1463-9076
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

References (32)

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Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO 2 reduction and enhanced proton reduction journal January 2019

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