Loading…
Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex
We introduce a new family of complexes with the general formula [Ru n (tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda2– being [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H +, which we find to be an impressive water...
Saved in:
| Published in: | Journal of the American Chemical Society 2015-08, Vol.137 (33), p.10786-10795 |
|---|---|
| Main Authors: | , , , , , , |
| Format: | Article |
| Language: | English |
| Subjects: | |
| Citations: | Items that this one cites Items that cite this one |
| Online Access: | Get full text |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| cited_by | cdi_FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093 |
|---|---|
| cites | cdi_FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093 |
| container_end_page | 10795 |
| container_issue | 33 |
| container_start_page | 10786 |
| container_title | Journal of the American Chemical Society |
| container_volume | 137 |
| creator | Matheu, Roc Ertem, Mehmed Z Benet-Buchholz, Jordi Coronado, Eugenio Batista, Victor S Sala, Xavier Llobet, Antoni |
| description | We introduce a new family of complexes with the general formula [Ru n (tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda2– being [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H +, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3 2+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H + can be generated potentiometrically, or voltammetrically, from 3 2+, and both coexist in solution. While complex 3 2+ is not catalytically active, the catalytic performance of complex 4H + is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50 000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H +, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation. |
| doi_str_mv | 10.1021/jacs.5b06541 |
| format | article |
| fullrecord | <record><control><sourceid>proquest_osti_</sourceid><recordid>TN_cdi_osti_scitechconnect_1226070</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1738479746</sourcerecordid><originalsourceid>FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093</originalsourceid><addsrcrecordid>eNptkEFr3DAQRkVISTbb3nIOJqce6mQkW5J9bEybBgJbQkqPYmTJxIttbSUZdvvrq2U3zSUnMejNNzOPkEsKNxQYvV1jG264BsFLekIWlDPIOWXilCwAgOWyEsU5uQhhncqSVfSMnDPBmChqWJDVwxQ9jm6w7Tygz356F92UPXucQmd9dudciCH7jTEVq21vMPbpv8GIw-6vNZneZZg9zVnjxs1gtx_Jhw6HYD8d3yX59f3bc_Mjf1zdPzRfH3MsOY95WkOYrqpRV7rmtTRcokAo0VSARac5aCjQAK2loNRQywupS10zg7SroC6W5PqQm9brVWj7aNuX1k2TbaOi6TqQkKDPB2jj3Z_ZhqjGPrR2GHCybg6KyqIqZS1LkdAvB7T1LgRvO7Xx_Yh-pyiovWe196yOnhN-dUye9WjNf_hV7NvofdfazX5KNt7P-gfpEIUJ</addsrcrecordid><sourcetype>Open Access Repository</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1738479746</pqid></control><display><type>article</type><title>Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex</title><source>American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)</source><creator>Matheu, Roc ; Ertem, Mehmed Z ; Benet-Buchholz, Jordi ; Coronado, Eugenio ; Batista, Victor S ; Sala, Xavier ; Llobet, Antoni</creator><creatorcontrib>Matheu, Roc ; Ertem, Mehmed Z ; Benet-Buchholz, Jordi ; Coronado, Eugenio ; Batista, Victor S ; Sala, Xavier ; Llobet, Antoni ; Brookhaven National Laboratory (BNL), Upton, NY (United States)</creatorcontrib><description>We introduce a new family of complexes with the general formula [Ru n (tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda2– being [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H +, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3 2+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H + can be generated potentiometrically, or voltammetrically, from 3 2+, and both coexist in solution. While complex 3 2+ is not catalytically active, the catalytic performance of complex 4H + is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50 000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H +, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.</description><identifier>ISSN: 0002-7863</identifier><identifier>EISSN: 1520-5126</identifier><identifier>DOI: 10.1021/jacs.5b06541</identifier><identifier>PMID: 26226390</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>electrocatalysis ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; intramolecular proton transfer ; redox properties ; Ru complexes ; seven coordination ; water oxidation catalysis ; water splitting</subject><ispartof>Journal of the American Chemical Society, 2015-08, Vol.137 (33), p.10786-10795</ispartof><rights>Copyright © American Chemical Society</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093</citedby><cites>FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>230,315,786,790,891,27957,27958</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26226390$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink><backlink>$$Uhttps://www.osti.gov/servlets/purl/1226070$$D View this record in Osti.gov$$Hfree_for_read</backlink></links><search><creatorcontrib>Matheu, Roc</creatorcontrib><creatorcontrib>Ertem, Mehmed Z</creatorcontrib><creatorcontrib>Benet-Buchholz, Jordi</creatorcontrib><creatorcontrib>Coronado, Eugenio</creatorcontrib><creatorcontrib>Batista, Victor S</creatorcontrib><creatorcontrib>Sala, Xavier</creatorcontrib><creatorcontrib>Llobet, Antoni</creatorcontrib><creatorcontrib>Brookhaven National Laboratory (BNL), Upton, NY (United States)</creatorcontrib><title>Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex</title><title>Journal of the American Chemical Society</title><addtitle>J. Am. Chem. Soc</addtitle><description>We introduce a new family of complexes with the general formula [Ru n (tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda2– being [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H +, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3 2+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H + can be generated potentiometrically, or voltammetrically, from 3 2+, and both coexist in solution. While complex 3 2+ is not catalytically active, the catalytic performance of complex 4H + is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50 000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H +, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.</description><subject>electrocatalysis</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>intramolecular proton transfer</subject><subject>redox properties</subject><subject>Ru complexes</subject><subject>seven coordination</subject><subject>water oxidation catalysis</subject><subject>water splitting</subject><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2015</creationdate><recordtype>article</recordtype><recordid>eNptkEFr3DAQRkVISTbb3nIOJqce6mQkW5J9bEybBgJbQkqPYmTJxIttbSUZdvvrq2U3zSUnMejNNzOPkEsKNxQYvV1jG264BsFLekIWlDPIOWXilCwAgOWyEsU5uQhhncqSVfSMnDPBmChqWJDVwxQ9jm6w7Tygz356F92UPXucQmd9dudciCH7jTEVq21vMPbpv8GIw-6vNZneZZg9zVnjxs1gtx_Jhw6HYD8d3yX59f3bc_Mjf1zdPzRfH3MsOY95WkOYrqpRV7rmtTRcokAo0VSARac5aCjQAK2loNRQywupS10zg7SroC6W5PqQm9brVWj7aNuX1k2TbaOi6TqQkKDPB2jj3Z_ZhqjGPrR2GHCybg6KyqIqZS1LkdAvB7T1LgRvO7Xx_Yh-pyiovWe196yOnhN-dUye9WjNf_hV7NvofdfazX5KNt7P-gfpEIUJ</recordid><startdate>20150826</startdate><enddate>20150826</enddate><creator>Matheu, Roc</creator><creator>Ertem, Mehmed Z</creator><creator>Benet-Buchholz, Jordi</creator><creator>Coronado, Eugenio</creator><creator>Batista, Victor S</creator><creator>Sala, Xavier</creator><creator>Llobet, Antoni</creator><general>American Chemical Society</general><general>American Chemical Society (ACS)</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>OIOZB</scope><scope>OTOTI</scope></search><sort><creationdate>20150826</creationdate><title>Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex</title><author>Matheu, Roc ; Ertem, Mehmed Z ; Benet-Buchholz, Jordi ; Coronado, Eugenio ; Batista, Victor S ; Sala, Xavier ; Llobet, Antoni</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2015</creationdate><topic>electrocatalysis</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>intramolecular proton transfer</topic><topic>redox properties</topic><topic>Ru complexes</topic><topic>seven coordination</topic><topic>water oxidation catalysis</topic><topic>water splitting</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Matheu, Roc</creatorcontrib><creatorcontrib>Ertem, Mehmed Z</creatorcontrib><creatorcontrib>Benet-Buchholz, Jordi</creatorcontrib><creatorcontrib>Coronado, Eugenio</creatorcontrib><creatorcontrib>Batista, Victor S</creatorcontrib><creatorcontrib>Sala, Xavier</creatorcontrib><creatorcontrib>Llobet, Antoni</creatorcontrib><creatorcontrib>Brookhaven National Laboratory (BNL), Upton, NY (United States)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV - Hybrid</collection><collection>OSTI.GOV</collection><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Matheu, Roc</au><au>Ertem, Mehmed Z</au><au>Benet-Buchholz, Jordi</au><au>Coronado, Eugenio</au><au>Batista, Victor S</au><au>Sala, Xavier</au><au>Llobet, Antoni</au><aucorp>Brookhaven National Laboratory (BNL), Upton, NY (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2015-08-26</date><risdate>2015</risdate><volume>137</volume><issue>33</issue><spage>10786</spage><epage>10795</epage><pages>10786-10795</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><notes>ObjectType-Article-1</notes><notes>SourceType-Scholarly Journals-1</notes><notes>ObjectType-Feature-2</notes><notes>content type line 23</notes><notes>USDOE Office of Science (SC), Basic Energy Sciences (BES)</notes><notes>BNL-108552-2015-JA</notes><notes>SC00112704</notes><abstract>We introduce a new family of complexes with the general formula [Ru n (tda)(py)2] m+ (n = 2, m = 0, 1; n = 3, m = 1, 2 +; n = 4, m = 2, 3 2+), with tda2– being [2,2′:6′,2″-terpyridine]-6,6″-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H +, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 3 2+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H + can be generated potentiometrically, or voltammetrically, from 3 2+, and both coexist in solution. While complex 3 2+ is not catalytically active, the catalytic performance of complex 4H + is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50 000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H +, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>26226390</pmid><doi>10.1021/jacs.5b06541</doi><tpages>10</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 0002-7863 |
| ispartof | Journal of the American Chemical Society, 2015-08, Vol.137 (33), p.10786-10795 |
| issn | 0002-7863 1520-5126 |
| language | eng |
| recordid | cdi_osti_scitechconnect_1226070 |
| source | American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list) |
| subjects | electrocatalysis INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY intramolecular proton transfer redox properties Ru complexes seven coordination water oxidation catalysis water splitting |
| title | Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex |
| url | http://sfxeu10.hosted.exlibrisgroup.com/loughborough?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2024-09-21T17%3A10%3A26IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_osti_&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Intramolecular%20Proton%20Transfer%20Boosts%20Water%20Oxidation%20Catalyzed%20by%20a%20Ru%20Complex&rft.jtitle=Journal%20of%20the%20American%20Chemical%20Society&rft.au=Matheu,%20Roc&rft.aucorp=Brookhaven%20National%20Laboratory%20(BNL),%20Upton,%20NY%20(United%20States)&rft.date=2015-08-26&rft.volume=137&rft.issue=33&rft.spage=10786&rft.epage=10795&rft.pages=10786-10795&rft.issn=0002-7863&rft.eissn=1520-5126&rft_id=info:doi/10.1021/jacs.5b06541&rft_dat=%3Cproquest_osti_%3E1738479746%3C/proquest_osti_%3E%3Cgrp_id%3Ecdi_FETCH-LOGICAL-a455t-2816df89ab8b9597d57a6a04ad80a3fb50b03ad0197611d1e537b4b92da1f8093%3C/grp_id%3E%3Coa%3E%3C/oa%3E%3Curl%3E%3C/url%3E&rft_id=info:oai/&rft_pqid=1738479746&rft_id=info:pmid/26226390&rfr_iscdi=true |