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

Abstract

Abstract:A series of microhydrated nickel carbonyls, Ni(CO) 3 (H 2 O) 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 leads to solvation at the carbonyl terminal. The formation of a water-ring network is achieved via a water trimer and is perfected at the tetramer. Spectroscopy combined with theory suggests that the water molecules prefer to antisymmetrically solvate the carbonyl terminals. The present findings would have important implications for fundamental understanding of the multifaceted mechanisms of the multibody interaction of water and carbon monoxide with transition metals.2

Sulfur substitution in a Ni(cyclam) derivative results in lower overpotential for CO2 reduction and enhanced proton reduction

“…The frequency observed for the Ni-CO species is in the same range as the stretching frequency observed for Ni(CO) 4 (2056 cm −1 ), suggesting the formation of a Ni 0 -CO species. 33,34 However, based on these experiments no statement about the exact nature of the reduced species can be made. Furthermore, this band is not observed when the experiments were performed in pure acetonitrile (non-catalytic conditions) or pure water (only H 2 formation).…”

Probing the Hydrogen Bonding in Microsolvated Clusters of Au1,2–(Solv)n(Solv = C2H5OH,n-C3H7OH;n= 1–3 for Au–;n=1 for Au2–)

“…Previous studies have shown that the polarity and number of solvent molecules have significant effects on the charge transfer and solvation structure between solute anions and solvent molecules. − Plenty of studies have shown that there are mainly two kinds of interactions: nonconventional hydrogen bonds (NHBs) and conventional hydrogen bonds (HBs) between the solute metal anions and solvent water molecules using infrared photodetachment spectrum and photoelectron spectroscopy method. − These two kinds of interaction compete with each other, and the dominant interaction changes in different solvent environments. However, the interaction between other solvent molecules and metal anions is rarely studied.…”

Dinitrogen Activation by Heteronuclear Bimetallic Cluster Anion FeV– in the Gas Phase

“…It had a two-dimensional imaging detector, and the density of the photoelectron in its three-dimensional framework was projected onto this The Abel Inverse Basis Set Expansion (BASEX) transformation method was applied to the initial three-dimensional distribution, and photoelectron spectra were acquired by reorganizing the corresponding three-dimensional images. The experimental results were corrected through the Au − anion, 33 and the recorded energy resolution from the current instrument was more than 5%.…”