Mo Insertion into the H 2 Bond in Mo x S y - + H 2 Reactions
A combined experimental and computational study of H reactions with small Mo S clusters ranging from subsulfide ( ∼ ) to hypersulfide ( > 2 ) is presented. Results suggest that the subsulfides react with H primarily by insertion of a more reduced Mo center into the H-H bond, forming a dihydride p...
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| Published in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 123; no. 33; pp. 7261 - 7269 |
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| Main Authors: | , , , , |
| Format: | Journal Article |
| Language: | English |
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United States
American Chemical Society
22-08-2019
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| Abstract | A combined experimental and computational study of H
reactions with small
Mo
S
clusters ranging from subsulfide (
∼
) to hypersulfide (
> 2
) is presented. Results suggest that the subsulfides react with H
primarily by insertion of a more reduced Mo center into the H-H bond, forming a dihydride product. We find that this reaction occurs up to Mo oxidation states of +4. For the subsulfides containing a second metal in a sufficiently low oxidation state, a second insertion of H
occurs, leading to a tetrahydride product. The reaction mechanisms of the sulfides are found to be very similar, albeit slightly higher energetically to those of the analogous oxosulfides that are also observed at low abundances in the experiments. In addition, the experimental results show an overall reduction of hypersulfides in the presence of H
, suggesting loss of H
S neutral molecules. |
|---|---|
| AbstractList | Not provided. A combined experimental and computational study of H reactions with small Mo S clusters ranging from subsulfide ( ∼ ) to hypersulfide ( > 2 ) is presented. Results suggest that the subsulfides react with H primarily by insertion of a more reduced Mo center into the H-H bond, forming a dihydride product. We find that this reaction occurs up to Mo oxidation states of +4. For the subsulfides containing a second metal in a sufficiently low oxidation state, a second insertion of H occurs, leading to a tetrahydride product. The reaction mechanisms of the sulfides are found to be very similar, albeit slightly higher energetically to those of the analogous oxosulfides that are also observed at low abundances in the experiments. In addition, the experimental results show an overall reduction of hypersulfides in the presence of H , suggesting loss of H S neutral molecules. |
| Author | Jarrold, Caroline Chick Nickson, Kathleen A Gupta, Ankur K Topolski, Josey E Raghavachari, Krishnan |
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| BackLink | https://www.ncbi.nlm.nih.gov/pubmed/31403804$$D View this record in MEDLINE/PubMed https://www.osti.gov/biblio/1609795$$D View this record in Osti.gov |
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| Cites_doi | 10.1021/jacs.6b05940 10.1002/celc.201800719 10.1016/S1381-1169(02)00418-1 10.1021/ja404523s 10.1021/jacs.5b03329 10.1016/S0039-6028(03)00957-9 10.1038/s41598-017-15622-z 10.1063/1.4830096 10.1063/1.475557 10.1039/C8SE00346G 10.1007/s11051-017-4072-7 10.1016/j.ijms.2018.09.019 10.1103/PhysRevB.85.195410 10.1021/ja201269b 10.1021/acscatal.5b02369 10.1063/1.3242294 10.1063/1.3463413 10.1103/PhysRevA.38.3098 10.1021/ja0504690 10.1007/s11244-017-0864-3 10.1063/1.3096414 10.1002/adma.201701955 10.1016/j.cej.2018.04.207 10.1021/ar990028j 10.1016/j.apmt.2016.02.001 10.1103/PhysRevB.37.785 10.1021/jacs.6b01377 10.1070/RCR4800 10.1021/jp510899m 10.1063/1.464913 10.1021/jp3119692 10.1007/BF01114537 10.1016/0021-9517(92)90166-F 10.1039/C7CP00636E 10.1016/j.apcatb.2018.04.068 10.1002/jcc.21759 10.1016/j.ccr.2018.07.019 10.1007/s12678-018-0485-z 10.1021/acs.nanolett.6b00569 10.1007/s00339-003-2419-7 10.1002/anie.200461698 10.1063/1.467146 10.1016/j.electacta.2018.06.135 10.1021/acscatal.6b01848 10.1063/1.1853379 10.1063/1.3382344 10.1039/c2cs35310e 10.1063/1.463096 10.1021/cg0700972 10.1021/acs.jpcc.8b08324 10.1039/C8RA01147H 10.1073/pnas.1316792110 10.1126/science.1141483 10.1021/acscatal.8b00883 10.1126/science.251.4990.175 10.1063/1.3635408 10.1016/j.cplett.2011.11.063 |
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| References | ref9/cit9 ref45/cit45 ref3/cit3 ref27/cit27 ref56/cit56 ref16/cit16 ref52/cit52 ref23/cit23 ref8/cit8 ref31/cit31 ref59/cit59 ref2/cit2 ref34/cit34 ref37/cit37 ref20/cit20 ref48/cit48 ref60/cit60 ref17/cit17 ref10/cit10 ref53/cit53 ref19/cit19 ref21/cit21 Somorjai G. A. (ref38/cit38) 1994 ref42/cit42 ref46/cit46 ref49/cit49 ref13/cit13 ref24/cit24 ref50/cit50 ref54/cit54 ref6/cit6 ref36/cit36 ref18/cit18 ref11/cit11 ref25/cit25 ref29/cit29 ref32/cit32 ref39/cit39 ref14/cit14 ref57/cit57 ref5/cit5 ref51/cit51 Zhang X. F. (ref35/cit35) 2018; 37 ref43/cit43 ref28/cit28 ref40/cit40 ref26/cit26 ref55/cit55 ref12/cit12 ref15/cit15 ref41/cit41 ref58/cit58 ref22/cit22 ref33/cit33 ref4/cit4 ref30/cit30 ref47/cit47 ref1/cit1 ref44/cit44 ref7/cit7 |
| References_xml | – ident: ref6/cit6 doi: 10.1021/jacs.6b05940 – ident: ref32/cit32 doi: 10.1002/celc.201800719 – ident: ref22/cit22 doi: 10.1016/S1381-1169(02)00418-1 – ident: ref11/cit11 doi: 10.1021/ja404523s – ident: ref50/cit50 – ident: ref25/cit25 doi: 10.1021/jacs.5b03329 – ident: ref21/cit21 doi: 10.1016/S0039-6028(03)00957-9 – ident: ref19/cit19 doi: 10.1038/s41598-017-15622-z – ident: ref41/cit41 doi: 10.1063/1.4830096 – ident: ref47/cit47 doi: 10.1063/1.475557 – ident: ref33/cit33 doi: 10.1039/C8SE00346G – ident: ref34/cit34 doi: 10.1007/s11051-017-4072-7 – ident: ref42/cit42 doi: 10.1016/j.ijms.2018.09.019 – ident: ref23/cit23 doi: 10.1103/PhysRevB.85.195410 – ident: ref9/cit9 doi: 10.1021/ja201269b – volume: 37 start-page: 497 year: 2018 ident: ref35/cit35 publication-title: Chinese Journal of Structural Chemistry contributor: fullname: Zhang X. F. – ident: ref28/cit28 doi: 10.1021/acscatal.5b02369 – ident: ref44/cit44 doi: 10.1063/1.3242294 – ident: ref46/cit46 doi: 10.1063/1.3463413 – ident: ref51/cit51 doi: 10.1103/PhysRevA.38.3098 – ident: ref8/cit8 doi: 10.1021/ja0504690 – ident: ref30/cit30 doi: 10.1007/s11244-017-0864-3 – ident: ref45/cit45 doi: 10.1063/1.3096414 – ident: ref26/cit26 doi: 10.1002/adma.201701955 – ident: ref3/cit3 doi: 10.1016/j.cej.2018.04.207 – ident: ref59/cit59 doi: 10.1021/ar990028j – ident: ref2/cit2 doi: 10.1016/j.apmt.2016.02.001 – ident: ref52/cit52 doi: 10.1103/PhysRevB.37.785 – ident: ref10/cit10 doi: 10.1021/jacs.6b01377 – ident: ref36/cit36 doi: 10.1070/RCR4800 – ident: ref24/cit24 doi: 10.1021/jp510899m – ident: ref53/cit53 doi: 10.1063/1.464913 – ident: ref48/cit48 doi: 10.1021/jp3119692 – ident: ref58/cit58 doi: 10.1007/BF01114537 – ident: ref15/cit15 doi: 10.1016/0021-9517(92)90166-F – ident: ref20/cit20 doi: 10.1039/C7CP00636E – ident: ref14/cit14 doi: 10.1016/j.apcatb.2018.04.068 – ident: ref55/cit55 doi: 10.1002/jcc.21759 – ident: ref1/cit1 doi: 10.1016/j.ccr.2018.07.019 – ident: ref4/cit4 doi: 10.1007/s12678-018-0485-z – ident: ref17/cit17 doi: 10.1021/acs.nanolett.6b00569 – ident: ref16/cit16 doi: 10.1007/s00339-003-2419-7 – ident: ref37/cit37 doi: 10.1002/anie.200461698 – ident: ref57/cit57 doi: 10.1063/1.467146 – ident: ref13/cit13 doi: 10.1016/j.electacta.2018.06.135 – ident: ref27/cit27 doi: 10.1021/acscatal.6b01848 – ident: ref40/cit40 doi: 10.1063/1.1853379 – ident: ref54/cit54 doi: 10.1063/1.3382344 – ident: ref7/cit7 doi: 10.1039/c2cs35310e – volume-title: Introduction to Surface Chemistry and Catalysis year: 1994 ident: ref38/cit38 contributor: fullname: Somorjai G. A. – ident: ref56/cit56 doi: 10.1063/1.463096 – ident: ref49/cit49 doi: 10.1021/cg0700972 – ident: ref31/cit31 doi: 10.1021/acs.jpcc.8b08324 – ident: ref18/cit18 doi: 10.1039/C8RA01147H – ident: ref12/cit12 doi: 10.1073/pnas.1316792110 – ident: ref5/cit5 doi: 10.1126/science.1141483 – ident: ref29/cit29 doi: 10.1021/acscatal.8b00883 – ident: ref60/cit60 doi: 10.1126/science.251.4990.175 – ident: ref39/cit39 doi: 10.1063/1.3635408 – ident: ref43/cit43 doi: 10.1016/j.cplett.2011.11.063 |
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| Snippet | A combined experimental and computational study of H
reactions with small
Mo
S
clusters ranging from subsulfide (
∼
) to hypersulfide (
> 2
) is presented.... Not provided. |
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| Title | Mo Insertion into the H 2 Bond in Mo x S y - + H 2 Reactions |
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