Kinetic Studies of the Reduction of [Co(dmgH)2(py)(Cl)] Revisited: Mechanisms, Products, and Implications
We report on a mechanistic investigation regarding the reduction of [CoIII(dmgH)2(py)(Cl)] (dmg = dimethylglyoxime) by several complementary techniques. The reduction of [CoIII(dmgH)2(py)(Cl)] was initiated by either electrochemical, photochemical, or pulse radiolytical techniques, and the corresp...
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| Veröffentlicht in: | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-06, Vol.118 (25), p.4382-4391 |
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| container_end_page | 4391 |
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| container_issue | 25 |
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| container_title | The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory |
| container_volume | 118 |
| creator | Kahnt, Axel Peuntinger, Katrin Dammann, Claudia Drewello, Thomas Hermann, Ralf Naumov, Sergej Abel, Bernd Guldi, Dirk M |
| description | We report on a mechanistic investigation regarding the reduction of [CoIII(dmgH)2(py)(Cl)] (dmg = dimethylglyoxime) by several complementary techniques. The reduction of [CoIII(dmgH)2(py)(Cl)] was initiated by either electrochemical, photochemical, or pulse radiolytical techniques, and the corresponding products were analyzed by ESI mass spectrometry. In addition, all of the rate constants for each step were determined. We have found solid experimental as well as theoretical evidence for the appearance of a dinuclear complex [CoIICoIII(dmgH)4(py)2(H2O)2]+ to be the final product of reduction, implying the initially reduced form of [CoIII(dmgH)2(py)(Cl)] undergoes a dimerization with the starting material in solution. |
| doi_str_mv | 10.1021/jp501947y |
| format | Article |
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The reduction of [CoIII(dmgH)2(py)(Cl)] was initiated by either electrochemical, photochemical, or pulse radiolytical techniques, and the corresponding products were analyzed by ESI mass spectrometry. In addition, all of the rate constants for each step were determined. We have found solid experimental as well as theoretical evidence for the appearance of a dinuclear complex [CoIICoIII(dmgH)4(py)2(H2O)2]+ to be the final product of reduction, implying the initially reduced form of [CoIII(dmgH)2(py)(Cl)] undergoes a dimerization with the starting material in solution.</description><identifier>ISSN: 1089-5639</identifier><identifier>EISSN: 1520-5215</identifier><identifier>DOI: 10.1021/jp501947y</identifier><identifier>PMID: 24818962</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Dimerization ; Mass spectrometry ; Photochemical ; Physical chemistry ; Rate constants ; Reduction ; Spectroscopy</subject><ispartof>The journal of physical chemistry. 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A, Molecules, spectroscopy, kinetics, environment, & general theory</title><addtitle>J. Phys. Chem. A</addtitle><description>We report on a mechanistic investigation regarding the reduction of [CoIII(dmgH)2(py)(Cl)] (dmg = dimethylglyoxime) by several complementary techniques. The reduction of [CoIII(dmgH)2(py)(Cl)] was initiated by either electrochemical, photochemical, or pulse radiolytical techniques, and the corresponding products were analyzed by ESI mass spectrometry. In addition, all of the rate constants for each step were determined. We have found solid experimental as well as theoretical evidence for the appearance of a dinuclear complex [CoIICoIII(dmgH)4(py)2(H2O)2]+ to be the final product of reduction, implying the initially reduced form of [CoIII(dmgH)2(py)(Cl)] undergoes a dimerization with the starting material in solution.</description><subject>Dimerization</subject><subject>Mass spectrometry</subject><subject>Photochemical</subject><subject>Physical chemistry</subject><subject>Rate constants</subject><subject>Reduction</subject><subject>Spectroscopy</subject><issn>1089-5639</issn><issn>1520-5215</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2014</creationdate><recordtype>article</recordtype><recordid>eNqFkU1LxDAQhoMo7rp68A9IL0IXrGaSfqTepKi7qCh-nERKmqRuln7ZtML-e1N23ZPgaYbhmQdmXoSOAZ8DJnCxbAIMsR-tdtAYAoK9gECwa3vMYi8IaTxCB8YsMcZAib-PRsRnwOKQjJG-05XqtHBeul5qZZw6d7qFcp6V7EWn62oYvCe1K8vP2ZS4zWrqJsX0wwLf2uhOyUvnQYkFr7QpzZnz1NbDou14JZ152RRa8MFjDtFezgujjjZ1gt5url-TmXf_eDtPru49Tn3WeZCDDBiDECgWTPokylWMKeQRz-wlIsxIJqQQmGCIRC58TjjPMhIJKVmWBXSC3LW3aeuvXpkuLbURqih4perepBCFBAc-hPh_1GI0AuoP1ukaFW1tTKvytGl1ydtVCjgdQki3IVj2ZKPts1LJLfn7dQucrgEuTLqs-7ayD_lD9APNeIzf</recordid><startdate>20140626</startdate><enddate>20140626</enddate><creator>Kahnt, Axel</creator><creator>Peuntinger, Katrin</creator><creator>Dammann, Claudia</creator><creator>Drewello, Thomas</creator><creator>Hermann, Ralf</creator><creator>Naumov, Sergej</creator><creator>Abel, Bernd</creator><creator>Guldi, Dirk M</creator><general>American Chemical Society</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20140626</creationdate><title>Kinetic Studies of the Reduction of [Co(dmgH)2(py)(Cl)] Revisited: Mechanisms, Products, and Implications</title><author>Kahnt, Axel ; Peuntinger, Katrin ; Dammann, Claudia ; Drewello, Thomas ; Hermann, Ralf ; Naumov, Sergej ; Abel, Bernd ; Guldi, Dirk M</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-a348t-1f1d58816130c8d427fe9031f7ab639c6b2bcdcc02017cfc4a2aabb27cdd8bb53</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2014</creationdate><topic>Dimerization</topic><topic>Mass spectrometry</topic><topic>Photochemical</topic><topic>Physical chemistry</topic><topic>Rate constants</topic><topic>Reduction</topic><topic>Spectroscopy</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kahnt, Axel</creatorcontrib><creatorcontrib>Peuntinger, Katrin</creatorcontrib><creatorcontrib>Dammann, Claudia</creatorcontrib><creatorcontrib>Drewello, Thomas</creatorcontrib><creatorcontrib>Hermann, Ralf</creatorcontrib><creatorcontrib>Naumov, Sergej</creatorcontrib><creatorcontrib>Abel, Bernd</creatorcontrib><creatorcontrib>Guldi, Dirk M</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Engineered Materials Abstracts</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Kahnt, Axel</au><au>Peuntinger, Katrin</au><au>Dammann, Claudia</au><au>Drewello, Thomas</au><au>Hermann, Ralf</au><au>Naumov, Sergej</au><au>Abel, Bernd</au><au>Guldi, Dirk M</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Kinetic Studies of the Reduction of [Co(dmgH)2(py)(Cl)] Revisited: Mechanisms, Products, and Implications</atitle><jtitle>The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory</jtitle><addtitle>J. Phys. Chem. A</addtitle><date>2014-06-26</date><risdate>2014</risdate><volume>118</volume><issue>25</issue><spage>4382</spage><epage>4391</epage><pages>4382-4391</pages><issn>1089-5639</issn><eissn>1520-5215</eissn><abstract>We report on a mechanistic investigation regarding the reduction of [CoIII(dmgH)2(py)(Cl)] (dmg = dimethylglyoxime) by several complementary techniques. The reduction of [CoIII(dmgH)2(py)(Cl)] was initiated by either electrochemical, photochemical, or pulse radiolytical techniques, and the corresponding products were analyzed by ESI mass spectrometry. In addition, all of the rate constants for each step were determined. We have found solid experimental as well as theoretical evidence for the appearance of a dinuclear complex [CoIICoIII(dmgH)4(py)2(H2O)2]+ to be the final product of reduction, implying the initially reduced form of [CoIII(dmgH)2(py)(Cl)] undergoes a dimerization with the starting material in solution.</abstract><cop>United States</cop><pub>American Chemical Society</pub><pmid>24818962</pmid><doi>10.1021/jp501947y</doi><tpages>10</tpages></addata></record> |
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| source | American Chemical Society Journals |
| subjects | Dimerization Mass spectrometry Photochemical Physical chemistry Rate constants Reduction Spectroscopy |
| title | Kinetic Studies of the Reduction of [Co(dmgH)2(py)(Cl)] Revisited: Mechanisms, Products, and Implications |
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