Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime
Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged CoI-diglyoxime complex, forming CoIIIH, was monitored via transient absorption. The second-order rate constant for CoIIIH formation is in the range (3.5−4.7) × 109 M−1 s−1, with proton transfer coupled t...
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| Veröffentlicht in: | Journal of the American Chemical Society 2010-12, Vol.132 (47), p.16774-16776 |
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| container_issue | 47 |
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| container_title | Journal of the American Chemical Society |
| container_volume | 132 |
| creator | Dempsey, Jillian L Winkler, Jay R Gray, Harry B |
| description | Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged CoI-diglyoxime complex, forming CoIIIH, was monitored via transient absorption. The second-order rate constant for CoIIIH formation is in the range (3.5−4.7) × 109 M−1 s−1, with proton transfer coupled to excited-state deactivation of the photoacid. CoIIIH is subsequently reduced by excess CoI-diglyoxime in solution to produce CoIIH (k red = 9.2 × 106 M−1 s−1), which is then protonated to yield CoII-diglyoxime and H2. |
| doi_str_mv | 10.1021/ja109351h |
| format | Article |
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The second-order rate constant for CoIIIH formation is in the range (3.5−4.7) × 109 M−1 s−1, with proton transfer coupled to excited-state deactivation of the photoacid. 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Am. Chem. Soc</addtitle><description>Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged CoI-diglyoxime complex, forming CoIIIH, was monitored via transient absorption. The second-order rate constant for CoIIIH formation is in the range (3.5−4.7) × 109 M−1 s−1, with proton transfer coupled to excited-state deactivation of the photoacid. CoIIIH is subsequently reduced by excess CoI-diglyoxime in solution to produce CoIIH (k red = 9.2 × 106 M−1 s−1), which is then protonated to yield CoII-diglyoxime and H2.</description><issn>0002-7863</issn><issn>1520-5126</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid/><recordid>eNo9j81KxDAURoMoOI4ufINsXFZzb_6a5TCMVhjRha5Lmt7YlraBtiP69o4org7f5nwcxq5B3IJAuOs8CCc1NCdsBRpFpgHNKVsJITCzuZHn7GKeu-NUmMOKbZ4oNH5s54GnyAvku4_UH5Y2jTxOaeCevzRpSe800uQXqnnxVU9tnUKqfJ8-24Eu2Vn0_UxXf1yzt_vd67bI9s8Pj9vNPvMooMlyZa2sKwk6YlDkbVCglAera20ckg4m2Mo5AnQ5GTJBxwpUFBWhMejkmt38en2Yyy4dpvH4VoIof7rL_275DVgOSek</recordid><startdate>20101201</startdate><enddate>20101201</enddate><creator>Dempsey, Jillian L</creator><creator>Winkler, Jay R</creator><creator>Gray, Harry B</creator><general>American Chemical Society</general><scope/></search><sort><creationdate>20101201</creationdate><title>Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime</title><author>Dempsey, Jillian L ; Winkler, Jay R ; Gray, Harry B</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a201h-84773db315f2c4ea7c4144a175d5692e5c6c7b99e1298e6e6c5fb14f0be266293</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Dempsey, Jillian L</creatorcontrib><creatorcontrib>Winkler, Jay R</creatorcontrib><creatorcontrib>Gray, Harry B</creatorcontrib><jtitle>Journal of the American Chemical Society</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Dempsey, Jillian L</au><au>Winkler, Jay R</au><au>Gray, Harry B</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime</atitle><jtitle>Journal of the American Chemical Society</jtitle><addtitle>J. Am. Chem. Soc</addtitle><date>2010-12-01</date><risdate>2010</risdate><volume>132</volume><issue>47</issue><spage>16774</spage><epage>16776</epage><pages>16774-16776</pages><issn>0002-7863</issn><eissn>1520-5126</eissn><abstract>Proton transfer from the triplet excited state of brominated naphthol to a difluoroboryl bridged CoI-diglyoxime complex, forming CoIIIH, was monitored via transient absorption. The second-order rate constant for CoIIIH formation is in the range (3.5−4.7) × 109 M−1 s−1, with proton transfer coupled to excited-state deactivation of the photoacid. CoIIIH is subsequently reduced by excess CoI-diglyoxime in solution to produce CoIIH (k red = 9.2 × 106 M−1 s−1), which is then protonated to yield CoII-diglyoxime and H2.</abstract><pub>American Chemical Society</pub><doi>10.1021/ja109351h</doi><tpages>3</tpages><oa>free_for_read</oa></addata></record> |
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| source | American Chemical Society Journals |
| title | Mechanism of H2 Evolution from a Photogenerated Hydridocobaloxime |
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