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Title: The activation of carbon dioxide by first row transition metals (Sc – Zn)

Abstract

The activation of CO2 by chloride-tagged first-row transition metal anions [ClM]- (M=Sc–Zn), was examined by mass spectrometry, quantum chemical calculations, and statistical analysis. The direct formation of [ClM(CO2)]- complexes was demonstrated in the reaction between [ClM] - and neutral CO2. In addition, the reverse reaction was investigated by energy-variable collisionally induced dissociation (CID) of the corresponding [ClM(CO2)]- anions generated in-source. Five different mono- and bi-dentate binding motifs present in the ion/CO2 complexes were identified by quantum chemical calculations and the relative stability of the each of these isomers was established and analyzed for all first-row transition metals based on the experimental and theoretical ion/molecule binding energies. It was found that the early first row transition metals form strong covalent bonds with the neutral CO2 molecule, while the late in particular copper and zinc are weakly bonded. Using simple valence bond Lewis diagrams, the binding motifs and their relative stabilities across the first row were described in a quantitative manner based on the electronic structure of the individual metals. This analysis provides an explanation for the change of most favorite bonding motif of the transition metals with CO2 along the 1st transition metal row. The nature of the activated CO2 complexmore » and the relationship between its stability and other structural and spectral properties was also analyzed by Principal Component Analysis (PCA) and Artificial Neural Networks.« less

Authors:
 [1];  [2]; ORCiD logo [3];  [1]
  1. University of Oslo
  2. National Hellenic Research Foundation
  3. BATTELLE (PACIFIC NW LAB)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1525460
Report Number(s):
PNNL-SA-135757
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Volume: 20; Journal Issue: 39
Country of Publication:
United States
Language:
English

Citation Formats

Blaziak, Kacper, Tzeli, Demeter, Xantheas, Sotiris S., and Uggerud, Einar. The activation of carbon dioxide by first row transition metals (Sc – Zn). United States: N. p., 2018. Web. doi:10.1039/c8cp04231d.
Blaziak, Kacper, Tzeli, Demeter, Xantheas, Sotiris S., & Uggerud, Einar. The activation of carbon dioxide by first row transition metals (Sc – Zn). United States. doi:10.1039/c8cp04231d.
Blaziak, Kacper, Tzeli, Demeter, Xantheas, Sotiris S., and Uggerud, Einar. Sun . "The activation of carbon dioxide by first row transition metals (Sc – Zn)". United States. doi:10.1039/c8cp04231d.
@article{osti_1525460,
title = {The activation of carbon dioxide by first row transition metals (Sc – Zn)},
author = {Blaziak, Kacper and Tzeli, Demeter and Xantheas, Sotiris S. and Uggerud, Einar},
abstractNote = {The activation of CO2 by chloride-tagged first-row transition metal anions [ClM]- (M=Sc–Zn), was examined by mass spectrometry, quantum chemical calculations, and statistical analysis. The direct formation of [ClM(CO2)]- complexes was demonstrated in the reaction between [ClM] - and neutral CO2. In addition, the reverse reaction was investigated by energy-variable collisionally induced dissociation (CID) of the corresponding [ClM(CO2)]- anions generated in-source. Five different mono- and bi-dentate binding motifs present in the ion/CO2 complexes were identified by quantum chemical calculations and the relative stability of the each of these isomers was established and analyzed for all first-row transition metals based on the experimental and theoretical ion/molecule binding energies. It was found that the early first row transition metals form strong covalent bonds with the neutral CO2 molecule, while the late in particular copper and zinc are weakly bonded. Using simple valence bond Lewis diagrams, the binding motifs and their relative stabilities across the first row were described in a quantitative manner based on the electronic structure of the individual metals. This analysis provides an explanation for the change of most favorite bonding motif of the transition metals with CO2 along the 1st transition metal row. The nature of the activated CO2 complex and the relationship between its stability and other structural and spectral properties was also analyzed by Principal Component Analysis (PCA) and Artificial Neural Networks.},
doi = {10.1039/c8cp04231d},
journal = {Physical Chemistry Chemical Physics},
number = 39,
volume = 20,
place = {United States},
year = {2018},
month = {10}
}

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