Electrochemical Proton Reductions Catalyzed by the Simpler Hexacoordinate Iron Compounds as Functional Mimics of the Active Site in [FeFe] Hydrogenase
Ligand-substitution reaction of [( μ -S 2 C 4 N 2 H 2 )Fe 2 (CO) 6 ] ( 1 ) generated a normal mono-substituted diiron dithiolate derivative [( μ -S 2 C 4 N 2 H 2 )Fe 2 (CO) 5 (PMe 3 )] ( 1P ) and a simpler hexacoordinate mononuclear compound [( μ -S 2 C 4 N 2 H 2 )Fe([CO) 2 (PMe 3 ) 2 ] ( 2 ) via di...
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| Veröffentlicht in: | Electrocatalysis 2018-09, Vol.9 (5), p.563-572 |
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| creator | Gao, Shang Liang, Qing-Cheng Duan, Qian Jiang, Da-Yong Zhao, Jian-Xun |
| description | Ligand-substitution reaction of [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
6
] (
1
) generated a normal mono-substituted diiron dithiolate derivative [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
5
(PMe
3
)] (
1P
) and a simpler hexacoordinate mononuclear compound [(
μ
-S
2
C
4
N
2
H
2
)Fe([CO)
2
(PMe
3
)
2
] (
2
) via distinct reactivity pathways under identical conditions.
1P
and
2
could act as the electrochemically functional mimics of the [2Fe] sub-cluster and the distal Fe moiety of the active site of [FeFe] hydrogenase. The electrochemical investigations showed that
2
catalyzed the production of hydrogen from weak acid (acetic acid, HOAc) via two catalytic processes with an initial metal-orbital based reduction. In contrast, the electrocatalytic reaction of
2
with stronger acid (trifluoroacetic acid, TFA) occurred via an initial ligand protonation, and proceeded through different pathways that involved distinct oxidation states of the catalyst. The most striking result obtained in this study was that the hydrogen formation by
2
from TFA occurred at a relatively low overpotential as small as −0.28 V. It could be rationalized by the exclusive employment of iron(II) and iron(I) redox levels in the catalytic cycle, which was consistent with the enzymatic process. The observations might shed light on some aspects of ways by which the model compounds catalyzed the reduction of protons.
Graphical Abstract |
| doi_str_mv | 10.1007/s12678-017-0453-z |
| format | Article |
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μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
6
] (
1
) generated a normal mono-substituted diiron dithiolate derivative [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
5
(PMe
3
)] (
1P
) and a simpler hexacoordinate mononuclear compound [(
μ
-S
2
C
4
N
2
H
2
)Fe([CO)
2
(PMe
3
)
2
] (
2
) via distinct reactivity pathways under identical conditions.
1P
and
2
could act as the electrochemically functional mimics of the [2Fe] sub-cluster and the distal Fe moiety of the active site of [FeFe] hydrogenase. The electrochemical investigations showed that
2
catalyzed the production of hydrogen from weak acid (acetic acid, HOAc) via two catalytic processes with an initial metal-orbital based reduction. In contrast, the electrocatalytic reaction of
2
with stronger acid (trifluoroacetic acid, TFA) occurred via an initial ligand protonation, and proceeded through different pathways that involved distinct oxidation states of the catalyst. The most striking result obtained in this study was that the hydrogen formation by
2
from TFA occurred at a relatively low overpotential as small as −0.28 V. It could be rationalized by the exclusive employment of iron(II) and iron(I) redox levels in the catalytic cycle, which was consistent with the enzymatic process. The observations might shed light on some aspects of ways by which the model compounds catalyzed the reduction of protons.
Graphical Abstract</description><identifier>ISSN: 1868-2529</identifier><identifier>EISSN: 1868-5994</identifier><identifier>DOI: 10.1007/s12678-017-0453-z</identifier><language>eng</language><publisher>New York: Springer US</publisher><subject>Acetic acid ; Acids ; Catalysis ; Chemistry ; Chemistry and Materials Science ; Electrochemistry ; Energy Systems ; Hydrogen production ; Hydrogenase ; Iron ; Iron compounds ; Ligands ; Original Research ; Oxidation ; Physical Chemistry ; Protonation ; Reduction ; Reduction (metal working) ; Substitution reactions</subject><ispartof>Electrocatalysis, 2018-09, Vol.9 (5), p.563-572</ispartof><rights>Springer Science+Business Media, LLC, part of Springer Nature 2018</rights><rights>Copyright Springer Science & Business Media 2018</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c353t-125d1a93cfc923b378878eee0ca0b4e2efacbc68538e723b85b937f45e0ee5273</citedby><cites>FETCH-LOGICAL-c353t-125d1a93cfc923b378878eee0ca0b4e2efacbc68538e723b85b937f45e0ee5273</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://link.springer.com/content/pdf/10.1007/s12678-017-0453-z$$EPDF$$P50$$Gspringer$$H</linktopdf><linktohtml>$$Uhttps://link.springer.com/10.1007/s12678-017-0453-z$$EHTML$$P50$$Gspringer$$H</linktohtml><link.rule.ids>314,776,780,27901,27902,41464,42533,51294</link.rule.ids></links><search><creatorcontrib>Gao, Shang</creatorcontrib><creatorcontrib>Liang, Qing-Cheng</creatorcontrib><creatorcontrib>Duan, Qian</creatorcontrib><creatorcontrib>Jiang, Da-Yong</creatorcontrib><creatorcontrib>Zhao, Jian-Xun</creatorcontrib><title>Electrochemical Proton Reductions Catalyzed by the Simpler Hexacoordinate Iron Compounds as Functional Mimics of the Active Site in [FeFe] Hydrogenase</title><title>Electrocatalysis</title><addtitle>Electrocatalysis</addtitle><description>Ligand-substitution reaction of [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
6
] (
1
) generated a normal mono-substituted diiron dithiolate derivative [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
5
(PMe
3
)] (
1P
) and a simpler hexacoordinate mononuclear compound [(
μ
-S
2
C
4
N
2
H
2
)Fe([CO)
2
(PMe
3
)
2
] (
2
) via distinct reactivity pathways under identical conditions.
1P
and
2
could act as the electrochemically functional mimics of the [2Fe] sub-cluster and the distal Fe moiety of the active site of [FeFe] hydrogenase. The electrochemical investigations showed that
2
catalyzed the production of hydrogen from weak acid (acetic acid, HOAc) via two catalytic processes with an initial metal-orbital based reduction. In contrast, the electrocatalytic reaction of
2
with stronger acid (trifluoroacetic acid, TFA) occurred via an initial ligand protonation, and proceeded through different pathways that involved distinct oxidation states of the catalyst. The most striking result obtained in this study was that the hydrogen formation by
2
from TFA occurred at a relatively low overpotential as small as −0.28 V. It could be rationalized by the exclusive employment of iron(II) and iron(I) redox levels in the catalytic cycle, which was consistent with the enzymatic process. The observations might shed light on some aspects of ways by which the model compounds catalyzed the reduction of protons.
Graphical Abstract</description><subject>Acetic acid</subject><subject>Acids</subject><subject>Catalysis</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Electrochemistry</subject><subject>Energy Systems</subject><subject>Hydrogen production</subject><subject>Hydrogenase</subject><subject>Iron</subject><subject>Iron compounds</subject><subject>Ligands</subject><subject>Original Research</subject><subject>Oxidation</subject><subject>Physical Chemistry</subject><subject>Protonation</subject><subject>Reduction</subject><subject>Reduction (metal working)</subject><subject>Substitution reactions</subject><issn>1868-2529</issn><issn>1868-5994</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2018</creationdate><recordtype>article</recordtype><recordid>eNp1kV1LwzAUhosoOOZ-gHcBr6v5aJb0cozNDSaKH1ciIU1Pt462mUkrbj_E32v2AV55bnII7_Nw4I2ia4JvCcbizhM6FDLGRMQ44SzenUU9Iocy5mmanJ92yml6GQ28X-MwLGVY8l70M6nAtM6aFdSl0RV6cra1DXqGvDNtaRuPxrrV1XYHOcq2qF0BeinrTQUOzeBbG2tdXja6BTR3gRvbemO7JvdIezTtmoMjaB_KoPfIFgfDKHx_7UUBKxv0PoUpfKDZNnd2CY32cBVdFLryMDi9_ehtOnkdz-LF4_18PFrEhnHWxoTynOiUmcKklGVMSCkkAGCjcZYAhUKbzAwlZxJECEiepUwUCQcMwKlg_ejm6N04-9mBb9Xadi4c7BXFgcBSEBZS5JgyznrvoFAbV9babRXBat-AOjagQgNq34DaBYYeGR-yzRLcn_l_6Bf4v4vi</recordid><startdate>20180901</startdate><enddate>20180901</enddate><creator>Gao, Shang</creator><creator>Liang, Qing-Cheng</creator><creator>Duan, Qian</creator><creator>Jiang, Da-Yong</creator><creator>Zhao, Jian-Xun</creator><general>Springer US</general><general>Springer Nature B.V</general><scope>AAYXX</scope><scope>CITATION</scope></search><sort><creationdate>20180901</creationdate><title>Electrochemical Proton Reductions Catalyzed by the Simpler Hexacoordinate Iron Compounds as Functional Mimics of the Active Site in [FeFe] Hydrogenase</title><author>Gao, Shang ; Liang, Qing-Cheng ; Duan, Qian ; Jiang, Da-Yong ; Zhao, Jian-Xun</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c353t-125d1a93cfc923b378878eee0ca0b4e2efacbc68538e723b85b937f45e0ee5273</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2018</creationdate><topic>Acetic acid</topic><topic>Acids</topic><topic>Catalysis</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Electrochemistry</topic><topic>Energy Systems</topic><topic>Hydrogen production</topic><topic>Hydrogenase</topic><topic>Iron</topic><topic>Iron compounds</topic><topic>Ligands</topic><topic>Original Research</topic><topic>Oxidation</topic><topic>Physical Chemistry</topic><topic>Protonation</topic><topic>Reduction</topic><topic>Reduction (metal working)</topic><topic>Substitution reactions</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gao, Shang</creatorcontrib><creatorcontrib>Liang, Qing-Cheng</creatorcontrib><creatorcontrib>Duan, Qian</creatorcontrib><creatorcontrib>Jiang, Da-Yong</creatorcontrib><creatorcontrib>Zhao, Jian-Xun</creatorcontrib><collection>CrossRef</collection><jtitle>Electrocatalysis</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gao, Shang</au><au>Liang, Qing-Cheng</au><au>Duan, Qian</au><au>Jiang, Da-Yong</au><au>Zhao, Jian-Xun</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Electrochemical Proton Reductions Catalyzed by the Simpler Hexacoordinate Iron Compounds as Functional Mimics of the Active Site in [FeFe] Hydrogenase</atitle><jtitle>Electrocatalysis</jtitle><stitle>Electrocatalysis</stitle><date>2018-09-01</date><risdate>2018</risdate><volume>9</volume><issue>5</issue><spage>563</spage><epage>572</epage><pages>563-572</pages><issn>1868-2529</issn><eissn>1868-5994</eissn><abstract>Ligand-substitution reaction of [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
6
] (
1
) generated a normal mono-substituted diiron dithiolate derivative [(
μ
-S
2
C
4
N
2
H
2
)Fe
2
(CO)
5
(PMe
3
)] (
1P
) and a simpler hexacoordinate mononuclear compound [(
μ
-S
2
C
4
N
2
H
2
)Fe([CO)
2
(PMe
3
)
2
] (
2
) via distinct reactivity pathways under identical conditions.
1P
and
2
could act as the electrochemically functional mimics of the [2Fe] sub-cluster and the distal Fe moiety of the active site of [FeFe] hydrogenase. The electrochemical investigations showed that
2
catalyzed the production of hydrogen from weak acid (acetic acid, HOAc) via two catalytic processes with an initial metal-orbital based reduction. In contrast, the electrocatalytic reaction of
2
with stronger acid (trifluoroacetic acid, TFA) occurred via an initial ligand protonation, and proceeded through different pathways that involved distinct oxidation states of the catalyst. The most striking result obtained in this study was that the hydrogen formation by
2
from TFA occurred at a relatively low overpotential as small as −0.28 V. It could be rationalized by the exclusive employment of iron(II) and iron(I) redox levels in the catalytic cycle, which was consistent with the enzymatic process. The observations might shed light on some aspects of ways by which the model compounds catalyzed the reduction of protons.
Graphical Abstract</abstract><cop>New York</cop><pub>Springer US</pub><doi>10.1007/s12678-017-0453-z</doi><tpages>10</tpages></addata></record> |
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| ispartof | Electrocatalysis, 2018-09, Vol.9 (5), p.563-572 |
| issn | 1868-2529 1868-5994 |
| language | eng |
| recordid | cdi_proquest_journals_2072308713 |
| source | SpringerLink Journals |
| subjects | Acetic acid Acids Catalysis Chemistry Chemistry and Materials Science Electrochemistry Energy Systems Hydrogen production Hydrogenase Iron Iron compounds Ligands Original Research Oxidation Physical Chemistry Protonation Reduction Reduction (metal working) Substitution reactions |
| title | Electrochemical Proton Reductions Catalyzed by the Simpler Hexacoordinate Iron Compounds as Functional Mimics of the Active Site in [FeFe] Hydrogenase |
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