Oxygen activation by a macrocyclic chromium complex. Mechanism of hydroperoxo-chromium(III) to oxo-chromium(V) transformation
The transformation of the hydroperoxo complex L1(H2O)CrOOH2+ (L1 = 1, 4 8, 11-tetraazacyclotetradecane) to an oxo-chromium(v) species is a first-order process throughout the pH range examined, 1.7 < pH < 9.2. The pH dependence of the rate constant (k1) yielded an apparent pKa of 5.6 for L1(H2O...
Gespeichert in:
| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2005-02 (3), p.556-560 |
|---|---|
| Hauptverfasser: | , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 560 |
|---|---|
| container_issue | 3 |
| container_start_page | 556 |
| container_title | Dalton transactions : an international journal of inorganic chemistry |
| container_volume | |
| creator | Pestovsky, Oleg Bakac, Andreja |
| description | The transformation of the hydroperoxo complex L1(H2O)CrOOH2+ (L1 = 1, 4 8, 11-tetraazacyclotetradecane) to an oxo-chromium(v) species is a first-order process throughout the pH range examined, 1.7 < pH < 9.2. The pH dependence of the rate constant (k1) yielded an apparent pKa of 5.6 for L1(H2O)CrOOH2+. In the acidic range, (pH 7.5, k(1)= 0.025 s(-1). No [H+]-dependence is observed within the two limiting regimes, clearly ruling out a simple attack by H+ at the hydroperoxo group. The temperature dependence of k1 in 0.020 M HClO4 yielded the activation parameters DeltaH++ = 53.7 kJ mol(-1) and DeltaS++ = -80.5 J mol(-1) K(-1). |
| doi_str_mv | 10.1039/b416194g |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_67384914</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>67384914</sourcerecordid><originalsourceid>FETCH-LOGICAL-c367t-dc04b8d58538e0729a669a7d5fe6369f3270e4e967859529c2e2c62b8a43036c3</originalsourceid><addsrcrecordid>eNpVkF1LwzAYhYMobk7BXyC5knlRzVeT5lKGH4PJbtTbkqbpVmmamrSyXvjfrW5TvHoPh4dzeA8A5xhdY0TlTcYwx5KtDsAYMyEiSSg7_NWEj8BJCG8IEYJicgxGOOZi0HgMPpebfmVqqHRbfqi2dDXMeqigVdo73euq1FCvvbNlZ6F2tqnM5ho-Gb1WdRksdAVc97l3jfFu46I9Op3P51ewdfCf-TpYXtWhcN7-dJ2Co0JVwZzt7gS83N89zx6jxfJhPrtdRJpy0Ua5RixL8jiJaWKQIFJxLpXI48JwymVBiUCGGclFEsuYSE0M0ZxkiWIUUa7pBFxucxvv3jsT2tSWQZuqUrVxXUi5oAmTmA3gdAsO34fgTZE2vrTK9ylG6ffU6X7qAb3YZXaZNfkfuNuWfgGEzXox</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>67384914</pqid></control><display><type>article</type><title>Oxygen activation by a macrocyclic chromium complex. Mechanism of hydroperoxo-chromium(III) to oxo-chromium(V) transformation</title><source>Royal Society of Chemistry Journals Archive (1841-2007)</source><source>MEDLINE</source><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Pestovsky, Oleg ; Bakac, Andreja</creator><creatorcontrib>Pestovsky, Oleg ; Bakac, Andreja</creatorcontrib><description>The transformation of the hydroperoxo complex L1(H2O)CrOOH2+ (L1 = 1, 4 8, 11-tetraazacyclotetradecane) to an oxo-chromium(v) species is a first-order process throughout the pH range examined, 1.7 < pH < 9.2. The pH dependence of the rate constant (k1) yielded an apparent pKa of 5.6 for L1(H2O)CrOOH2+. In the acidic range, (pH <4), the value of k1 is 0.191 s(-1). At the other extreme, pH >7.5, k(1)= 0.025 s(-1). No [H+]-dependence is observed within the two limiting regimes, clearly ruling out a simple attack by H+ at the hydroperoxo group. The temperature dependence of k1 in 0.020 M HClO4 yielded the activation parameters DeltaH++ = 53.7 kJ mol(-1) and DeltaS++ = -80.5 J mol(-1) K(-1).</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/b416194g</identifier><identifier>PMID: 15672201</identifier><language>eng</language><publisher>England</publisher><subject>Chromium - chemistry ; Electron Spin Resonance Spectroscopy ; Hydrogen Peroxide - chemistry ; Hydrogen-Ion Concentration ; Macrocyclic Compounds - chemistry ; Macrocyclic Compounds - metabolism ; Oxidation-Reduction ; Oxygen - chemistry ; Oxygen - metabolism ; Temperature</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2005-02 (3), p.556-560</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c367t-dc04b8d58538e0729a669a7d5fe6369f3270e4e967859529c2e2c62b8a43036c3</citedby><cites>FETCH-LOGICAL-c367t-dc04b8d58538e0729a669a7d5fe6369f3270e4e967859529c2e2c62b8a43036c3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,2818,27901,27902</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15672201$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Pestovsky, Oleg</creatorcontrib><creatorcontrib>Bakac, Andreja</creatorcontrib><title>Oxygen activation by a macrocyclic chromium complex. Mechanism of hydroperoxo-chromium(III) to oxo-chromium(V) transformation</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>The transformation of the hydroperoxo complex L1(H2O)CrOOH2+ (L1 = 1, 4 8, 11-tetraazacyclotetradecane) to an oxo-chromium(v) species is a first-order process throughout the pH range examined, 1.7 < pH < 9.2. The pH dependence of the rate constant (k1) yielded an apparent pKa of 5.6 for L1(H2O)CrOOH2+. In the acidic range, (pH <4), the value of k1 is 0.191 s(-1). At the other extreme, pH >7.5, k(1)= 0.025 s(-1). No [H+]-dependence is observed within the two limiting regimes, clearly ruling out a simple attack by H+ at the hydroperoxo group. The temperature dependence of k1 in 0.020 M HClO4 yielded the activation parameters DeltaH++ = 53.7 kJ mol(-1) and DeltaS++ = -80.5 J mol(-1) K(-1).</description><subject>Chromium - chemistry</subject><subject>Electron Spin Resonance Spectroscopy</subject><subject>Hydrogen Peroxide - chemistry</subject><subject>Hydrogen-Ion Concentration</subject><subject>Macrocyclic Compounds - chemistry</subject><subject>Macrocyclic Compounds - metabolism</subject><subject>Oxidation-Reduction</subject><subject>Oxygen - chemistry</subject><subject>Oxygen - metabolism</subject><subject>Temperature</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpVkF1LwzAYhYMobk7BXyC5knlRzVeT5lKGH4PJbtTbkqbpVmmamrSyXvjfrW5TvHoPh4dzeA8A5xhdY0TlTcYwx5KtDsAYMyEiSSg7_NWEj8BJCG8IEYJicgxGOOZi0HgMPpebfmVqqHRbfqi2dDXMeqigVdo73euq1FCvvbNlZ6F2tqnM5ho-Gb1WdRksdAVc97l3jfFu46I9Op3P51ewdfCf-TpYXtWhcN7-dJ2Co0JVwZzt7gS83N89zx6jxfJhPrtdRJpy0Ua5RixL8jiJaWKQIFJxLpXI48JwymVBiUCGGclFEsuYSE0M0ZxkiWIUUa7pBFxucxvv3jsT2tSWQZuqUrVxXUi5oAmTmA3gdAsO34fgTZE2vrTK9ylG6ffU6X7qAb3YZXaZNfkfuNuWfgGEzXox</recordid><startdate>20050207</startdate><enddate>20050207</enddate><creator>Pestovsky, Oleg</creator><creator>Bakac, Andreja</creator><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20050207</creationdate><title>Oxygen activation by a macrocyclic chromium complex. Mechanism of hydroperoxo-chromium(III) to oxo-chromium(V) transformation</title><author>Pestovsky, Oleg ; Bakac, Andreja</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c367t-dc04b8d58538e0729a669a7d5fe6369f3270e4e967859529c2e2c62b8a43036c3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2005</creationdate><topic>Chromium - chemistry</topic><topic>Electron Spin Resonance Spectroscopy</topic><topic>Hydrogen Peroxide - chemistry</topic><topic>Hydrogen-Ion Concentration</topic><topic>Macrocyclic Compounds - chemistry</topic><topic>Macrocyclic Compounds - metabolism</topic><topic>Oxidation-Reduction</topic><topic>Oxygen - chemistry</topic><topic>Oxygen - metabolism</topic><topic>Temperature</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Pestovsky, Oleg</creatorcontrib><creatorcontrib>Bakac, Andreja</creatorcontrib><collection>Medline</collection><collection>MEDLINE</collection><collection>MEDLINE (Ovid)</collection><collection>MEDLINE</collection><collection>MEDLINE</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Pestovsky, Oleg</au><au>Bakac, Andreja</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Oxygen activation by a macrocyclic chromium complex. Mechanism of hydroperoxo-chromium(III) to oxo-chromium(V) transformation</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2005-02-07</date><risdate>2005</risdate><issue>3</issue><spage>556</spage><epage>560</epage><pages>556-560</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>The transformation of the hydroperoxo complex L1(H2O)CrOOH2+ (L1 = 1, 4 8, 11-tetraazacyclotetradecane) to an oxo-chromium(v) species is a first-order process throughout the pH range examined, 1.7 < pH < 9.2. The pH dependence of the rate constant (k1) yielded an apparent pKa of 5.6 for L1(H2O)CrOOH2+. In the acidic range, (pH <4), the value of k1 is 0.191 s(-1). At the other extreme, pH >7.5, k(1)= 0.025 s(-1). No [H+]-dependence is observed within the two limiting regimes, clearly ruling out a simple attack by H+ at the hydroperoxo group. The temperature dependence of k1 in 0.020 M HClO4 yielded the activation parameters DeltaH++ = 53.7 kJ mol(-1) and DeltaS++ = -80.5 J mol(-1) K(-1).</abstract><cop>England</cop><pmid>15672201</pmid><doi>10.1039/b416194g</doi><tpages>5</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2005-02 (3), p.556-560 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_67384914 |
| source | Royal Society of Chemistry Journals Archive (1841-2007); MEDLINE; Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Chromium - chemistry Electron Spin Resonance Spectroscopy Hydrogen Peroxide - chemistry Hydrogen-Ion Concentration Macrocyclic Compounds - chemistry Macrocyclic Compounds - metabolism Oxidation-Reduction Oxygen - chemistry Oxygen - metabolism Temperature |
| title | Oxygen activation by a macrocyclic chromium complex. Mechanism of hydroperoxo-chromium(III) to oxo-chromium(V) transformation |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-02-05T07%3A49%3A46IST&url_ver=Z39.88-2004&url_ctx_fmt=infofi/fmt:kev:mtx:ctx&rfr_id=info:sid/primo.exlibrisgroup.com:primo3-Article-proquest_cross&rft_val_fmt=info:ofi/fmt:kev:mtx:journal&rft.genre=article&rft.atitle=Oxygen%20activation%20by%20a%20macrocyclic%20chromium%20complex.%20Mechanism%20of%20hydroperoxo-chromium(III)%20to%20oxo-chromium(V)%20transformation&rft.jtitle=Dalton%20transactions%20:%20an%20international%20journal%20of%20inorganic%20chemistry&rft.au=Pestovsky,%20Oleg&rft.date=2005-02-07&rft.issue=3&rft.spage=556&rft.epage=560&rft.pages=556-560&rft.issn=1477-9226&rft.eissn=1477-9234&rft_id=info:doi/10.1039/b416194g&rft_dat=%3Cproquest_cross%3E67384914%3C/proquest_cross%3E%3Curl%3E%3C/url%3E&disable_directlink=true&sfx.directlink=off&sfx.report_link=0&rft_id=info:oai/&rft_pqid=67384914&rft_id=info:pmid/15672201&rfr_iscdi=true |