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Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)

[Image: see text] Molybdenum sulfides are considered a promising and inexpensive alternative to platinum as a catalyst for the hydrogen evolution reaction. In this study, we perform collision-induced dissociation experiments in the gas phase with the halogenated molybdenum sulfides [Mo(3)S(7)Cl(6)](...

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Autores principales: Pritzi, Marco, Pascher, Tobias F., Grutza, Marie-Luise, Kurz, Philipp, Ončák, Milan, Beyer, Martin K.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2022
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9460775/
https://www.ncbi.nlm.nih.gov/pubmed/35904429
http://dx.doi.org/10.1021/jasms.2c00162
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author Pritzi, Marco
Pascher, Tobias F.
Grutza, Marie-Luise
Kurz, Philipp
Ončák, Milan
Beyer, Martin K.
author_facet Pritzi, Marco
Pascher, Tobias F.
Grutza, Marie-Luise
Kurz, Philipp
Ončák, Milan
Beyer, Martin K.
author_sort Pritzi, Marco
collection PubMed
description [Image: see text] Molybdenum sulfides are considered a promising and inexpensive alternative to platinum as a catalyst for the hydrogen evolution reaction. In this study, we perform collision-induced dissociation experiments in the gas phase with the halogenated molybdenum sulfides [Mo(3)S(7)Cl(6)](2–), [Mo(3)S(7)Br(6)](2–), and [Mo(3)S(7)I(6)](2–). We show that the first fragmentation step for all three dianions is charge separation via loss of a halide ion. As a second step, further halogen loss competes with the dissociation of a disulfur molecule, whereas the former becomes energetically more favorable and the latter becomes less favorable from chlorine via bromine to iodine. We show that the leaving S(2) group is composed of sulfur atoms from two bridging groups. These decomposition pathways differ drastically from the pure [Mo(3)S(13)](2–) clusters. The obtained insight into preferred dissociation pathways of molybdenum sulfides illustrate possible reaction pathways during the activation of these substances in a catalytic environment.
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spelling pubmed-94607752022-09-10 Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I) Pritzi, Marco Pascher, Tobias F. Grutza, Marie-Luise Kurz, Philipp Ončák, Milan Beyer, Martin K. J Am Soc Mass Spectrom [Image: see text] Molybdenum sulfides are considered a promising and inexpensive alternative to platinum as a catalyst for the hydrogen evolution reaction. In this study, we perform collision-induced dissociation experiments in the gas phase with the halogenated molybdenum sulfides [Mo(3)S(7)Cl(6)](2–), [Mo(3)S(7)Br(6)](2–), and [Mo(3)S(7)I(6)](2–). We show that the first fragmentation step for all three dianions is charge separation via loss of a halide ion. As a second step, further halogen loss competes with the dissociation of a disulfur molecule, whereas the former becomes energetically more favorable and the latter becomes less favorable from chlorine via bromine to iodine. We show that the leaving S(2) group is composed of sulfur atoms from two bridging groups. These decomposition pathways differ drastically from the pure [Mo(3)S(13)](2–) clusters. The obtained insight into preferred dissociation pathways of molybdenum sulfides illustrate possible reaction pathways during the activation of these substances in a catalytic environment. American Chemical Society 2022-07-29 2022-09-07 /pmc/articles/PMC9460775/ /pubmed/35904429 http://dx.doi.org/10.1021/jasms.2c00162 Text en © 2022 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by/4.0/Permits the broadest form of re-use including for commercial purposes, provided that author attribution and integrity are maintained (https://creativecommons.org/licenses/by/4.0/).
spellingShingle Pritzi, Marco
Pascher, Tobias F.
Grutza, Marie-Luise
Kurz, Philipp
Ončák, Milan
Beyer, Martin K.
Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)
title Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)
title_full Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)
title_fullStr Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)
title_full_unstemmed Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)
title_short Decomposition of Halogenated Molybdenum Sulfide Dianions [Mo(3)S(7)X(6)](2–) (X = Cl, Br, I)
title_sort decomposition of halogenated molybdenum sulfide dianions [mo(3)s(7)x(6)](2–) (x = cl, br, i)
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9460775/
https://www.ncbi.nlm.nih.gov/pubmed/35904429
http://dx.doi.org/10.1021/jasms.2c00162
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