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Title: Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments

Abstract

We present that recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y ≥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with η2- acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. In conclusion, the results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the π orbitals in ethylene.

Authors:
 [1];  [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Indiana Univ., Bloomington, IN (United States)
Publication Date:
Research Org.:
Indiana Univ., Bloomington, IN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1512951
Alternate Identifier(s):
OSTI ID: 1419825
Grant/Contract Number:  
FG02-07ER15889
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 5; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schaugaard, Richard N., Topolski, Josey E., Ray, Manisha, Raghavachari, Krishnan, and Jarrold, Caroline Chick. Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments. United States: N. p., 2018. Web. doi:10.1063/1.5008264.
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Schaugaard, Richard N., Topolski, Josey E., Ray, Manisha, Raghavachari, Krishnan, & Jarrold, Caroline Chick. Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments. United States. https://doi.org/10.1063/1.5008264
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Schaugaard, Richard N., Topolski, Josey E., Ray, Manisha, Raghavachari, Krishnan, and Jarrold, Caroline Chick. Wed . "Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments". United States. https://doi.org/10.1063/1.5008264. https://www.osti.gov/servlets/purl/1512951.
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@article{osti_1512951,
title = {Insight into ethylene interactions with molybdenum suboxide cluster anions from photoelectron spectra of chemifragments},
author = {Schaugaard, Richard N. and Topolski, Josey E. and Ray, Manisha and Raghavachari, Krishnan and Jarrold, Caroline Chick},
abstractNote = {We present that recent studies on reactions between MoxOy- cluster anions and H2O/C2H4 mixtures revealed a complex web of addition, hydrogen evolution, and chemifragmentation reactions, with chemifragments unambiguously connected to cluster reactions with C2H4. To gain insight into the molecular-scale interactions along the chemifragmentation pathways, the anion photoelectron (PE) spectra of MoC2H2-, MoC4H4-, MoOC2H2-, and MoO2C2H2- formed directly in MoxOy- + C2H4 (x > 1; y ≥ x) reactions, along with supporting CCSD(T) and density functional theory calculations, are presented and analyzed. The complexes have spectra that are all consistent with η2- acetylene complexes, though for all but MoC4H4-, the possibility that vinylidene complexes are also present cannot be definitively ruled out. Structures that are consistent with the PE spectrum of MoC2H2- differ from the lowest energy structure, suggesting that the fragment formation is under kinetic control. The PE spectrum of MoO2C2H2- additionally exhibits evidence that photodissociation to MoO2- + C2H2 may be occurring. In conclusion, the results suggest that oxidative dehydrogenation of ethylene is initiated by Lewis acid/base interactions between the Mo centers in larger clusters and the π orbitals in ethylene.},
doi = {10.1063/1.5008264},
journal = {Journal of Chemical Physics},
number = 5,
volume = 148,
place = {United States},
year = {Wed Feb 07 00:00:00 EST 2018},
month = {Wed Feb 07 00:00:00 EST 2018}
}
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https://doi.org/10.1063/1.5008264
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Cited by: 15 works
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Figures / Tables:

FIG. 1 FIG. 1: Mass spectra in the mono-98Mo complex mass range. The dotted trace shows the initial mass distribution, with the solid trace showing the distribution following cluster reactions with C2H4. The PE spectra of the species labeled in bold face are shown in Fig. 2.
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      Figures / Tables found in this record:

      FIG. 1 (p. 4)figure
      FIG. 2 (p. 5)figure
      TABLE I (p. 6)table
      FIG. 3 (p. 7)figure
      FIG. 4 (p. 8)figure
      FIG. 5 (p. 9)figure
      FIG. 6 (p. 10)figure
      TABLE II (p. 11)table
      TABLE III (p. 11)table
      TABLE IV (p. 12)table
      TABLE V (p. 12)table
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