Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism
The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the en...
Gespeichert in:
| Veröffentlicht in: | Angewandte Chemie International Edition 2016-09, Vol.55 (38), p.11503-11506 |
|---|---|
| Hauptverfasser: | , , , |
| Format: | Artikel |
| Sprache: | eng |
| Schlagworte: | |
| Online-Zugang: | Volltext |
| Tags: |
Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
|
| container_end_page | 11506 |
|---|---|
| container_issue | 38 |
| container_start_page | 11503 |
| container_title | Angewandte Chemie International Edition |
| container_volume | 55 |
| creator | Demissie, Taye B. Garabato, Brady D. Ruud, Kenneth Kozlowski, Pawel M. |
| description | The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.
Of relative importance: The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical. This reaction mechanism is a consequence of relativistic effects, and constitutes the first example of relativity being decisive for the nature of an enzymatic reaction mechanism. SOC=spin–orbit coupling. |
| doi_str_mv | 10.1002/anie.201606001 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1817559693</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>1908276054</sourcerecordid><originalsourceid>FETCH-LOGICAL-c5821-5285fee9cb46b3854c7329b2f9621f9532e717c1e7f401a73e0a2528d31da05d3</originalsourceid><addsrcrecordid>eNqFkc2L1DAYxoso7odePUrBi5eOeZPmy9syzq4L2xFEURYkpOlbJmunXZPWtf-9GWcdxIOe3kB-z8MDvyx7BmQBhNBXtve4oAQEEYTAg-wYOIWCSckepnfJWCEVh6PsJMabxCtFxOPsiEoOhBN9nH2pMLgpzHmF42bu7OiHPq_nfDnUthvTCcH3g2_i6_w97r6_-zh6l6_aFt0Y8zfejXbEfNxgAqz7la_QbdKwuH2SPWptF_Hp_T3NPp6vPizfFlfvLi6XZ1eF4yrN5VTxFlG7uhQ1U7x0klFd01YLCq3mjKIE6QBlWxKwkiGxNIUaBo0lvGGn2ct9720Yvk0YR7P10WHX2R6HKRpQIDnXQrOEvvgLvRmm0Kd1BjRRVArCy39SCoTUmkmRqMWecmGIMWBrboPf2jAbIGanx-z0mIOeFHh-XzvVW2wO-G8fCdB74M53OP-nzpytL1d_lhf7bDKEPw5ZG74aIZnk5tP6wlSgz68_V9dmzX4CD3OpMw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1816799376</pqid></control><display><type>article</type><title>Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism</title><source>Wiley Online Library Journals Frontfile Complete</source><creator>Demissie, Taye B. ; Garabato, Brady D. ; Ruud, Kenneth ; Kozlowski, Pawel M.</creator><creatorcontrib>Demissie, Taye B. ; Garabato, Brady D. ; Ruud, Kenneth ; Kozlowski, Pawel M.</creatorcontrib><description>The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.
Of relative importance: The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical. This reaction mechanism is a consequence of relativistic effects, and constitutes the first example of relativity being decisive for the nature of an enzymatic reaction mechanism. SOC=spin–orbit coupling.</description><edition>International ed. in English</edition><identifier>ISSN: 1433-7851</identifier><identifier>EISSN: 1521-3773</identifier><identifier>DOI: 10.1002/anie.201606001</identifier><identifier>PMID: 27510509</identifier><identifier>CODEN: ACIEAY</identifier><language>eng</language><publisher>Germany: Blackwell Publishing Ltd</publisher><subject>Chemical bonds ; Cobalt ; computational chemistry ; Corrinoids ; Crystal structure ; density functional calculations ; enzyme catalysis ; Mercury ; Methylation ; Reaction mechanisms ; Relativism ; Relativistic effects ; Relativity ; Spin-orbit interactions ; transition states</subject><ispartof>Angewandte Chemie International Edition, 2016-09, Vol.55 (38), p.11503-11506</ispartof><rights>2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.</rights><rights>2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c5821-5285fee9cb46b3854c7329b2f9621f9532e717c1e7f401a73e0a2528d31da05d3</citedby><cites>FETCH-LOGICAL-c5821-5285fee9cb46b3854c7329b2f9621f9532e717c1e7f401a73e0a2528d31da05d3</cites><orcidid>0000-0001-8735-4933 ; 0000-0003-1006-8482</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fanie.201606001$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fanie.201606001$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27903,27904,45553,45554</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/27510509$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Demissie, Taye B.</creatorcontrib><creatorcontrib>Garabato, Brady D.</creatorcontrib><creatorcontrib>Ruud, Kenneth</creatorcontrib><creatorcontrib>Kozlowski, Pawel M.</creatorcontrib><title>Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism</title><title>Angewandte Chemie International Edition</title><addtitle>Angew. Chem. Int. Ed</addtitle><description>The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.
Of relative importance: The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical. This reaction mechanism is a consequence of relativistic effects, and constitutes the first example of relativity being decisive for the nature of an enzymatic reaction mechanism. SOC=spin–orbit coupling.</description><subject>Chemical bonds</subject><subject>Cobalt</subject><subject>computational chemistry</subject><subject>Corrinoids</subject><subject>Crystal structure</subject><subject>density functional calculations</subject><subject>enzyme catalysis</subject><subject>Mercury</subject><subject>Methylation</subject><subject>Reaction mechanisms</subject><subject>Relativism</subject><subject>Relativistic effects</subject><subject>Relativity</subject><subject>Spin-orbit interactions</subject><subject>transition states</subject><issn>1433-7851</issn><issn>1521-3773</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkc2L1DAYxoso7odePUrBi5eOeZPmy9syzq4L2xFEURYkpOlbJmunXZPWtf-9GWcdxIOe3kB-z8MDvyx7BmQBhNBXtve4oAQEEYTAg-wYOIWCSckepnfJWCEVh6PsJMabxCtFxOPsiEoOhBN9nH2pMLgpzHmF42bu7OiHPq_nfDnUthvTCcH3g2_i6_w97r6_-zh6l6_aFt0Y8zfejXbEfNxgAqz7la_QbdKwuH2SPWptF_Hp_T3NPp6vPizfFlfvLi6XZ1eF4yrN5VTxFlG7uhQ1U7x0klFd01YLCq3mjKIE6QBlWxKwkiGxNIUaBo0lvGGn2ct9720Yvk0YR7P10WHX2R6HKRpQIDnXQrOEvvgLvRmm0Kd1BjRRVArCy39SCoTUmkmRqMWecmGIMWBrboPf2jAbIGanx-z0mIOeFHh-XzvVW2wO-G8fCdB74M53OP-nzpytL1d_lhf7bDKEPw5ZG74aIZnk5tP6wlSgz68_V9dmzX4CD3OpMw</recordid><startdate>20160912</startdate><enddate>20160912</enddate><creator>Demissie, Taye B.</creator><creator>Garabato, Brady D.</creator><creator>Ruud, Kenneth</creator><creator>Kozlowski, Pawel M.</creator><general>Blackwell Publishing Ltd</general><general>Wiley Subscription Services, Inc</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7TM</scope><scope>K9.</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0001-8735-4933</orcidid><orcidid>https://orcid.org/0000-0003-1006-8482</orcidid></search><sort><creationdate>20160912</creationdate><title>Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism</title><author>Demissie, Taye B. ; Garabato, Brady D. ; Ruud, Kenneth ; Kozlowski, Pawel M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c5821-5285fee9cb46b3854c7329b2f9621f9532e717c1e7f401a73e0a2528d31da05d3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Chemical bonds</topic><topic>Cobalt</topic><topic>computational chemistry</topic><topic>Corrinoids</topic><topic>Crystal structure</topic><topic>density functional calculations</topic><topic>enzyme catalysis</topic><topic>Mercury</topic><topic>Methylation</topic><topic>Reaction mechanisms</topic><topic>Relativism</topic><topic>Relativistic effects</topic><topic>Relativity</topic><topic>Spin-orbit interactions</topic><topic>transition states</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Demissie, Taye B.</creatorcontrib><creatorcontrib>Garabato, Brady D.</creatorcontrib><creatorcontrib>Ruud, Kenneth</creatorcontrib><creatorcontrib>Kozlowski, Pawel M.</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>Nucleic Acids Abstracts</collection><collection>ProQuest Health & Medical Complete (Alumni)</collection><collection>MEDLINE - Academic</collection><jtitle>Angewandte Chemie International Edition</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Demissie, Taye B.</au><au>Garabato, Brady D.</au><au>Ruud, Kenneth</au><au>Kozlowski, Pawel M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism</atitle><jtitle>Angewandte Chemie International Edition</jtitle><addtitle>Angew. Chem. Int. Ed</addtitle><date>2016-09-12</date><risdate>2016</risdate><volume>55</volume><issue>38</issue><spage>11503</spage><epage>11506</epage><pages>11503-11506</pages><issn>1433-7851</issn><eissn>1521-3773</eissn><coden>ACIEAY</coden><abstract>The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical, in contrast to previously proposed reaction mechanisms. This reaction mechanism is a consequence of relativistic effects that lower the energies of the mercury 6p1/2 and 6p3/2 orbitals, making them energetically accessible for chemical bonding. In the absence of spin–orbit coupling, the predicted reaction mechanism is qualitatively different. This is the first example of relativity being decisive for the nature of an observed enzymatic reaction mechanism.
Of relative importance: The methylation of HgII(SCH3)2 by corrinoid‐based methyl donors proceeds in a concerted manner through a single transition state by transfer of a methyl radical. This reaction mechanism is a consequence of relativistic effects, and constitutes the first example of relativity being decisive for the nature of an enzymatic reaction mechanism. SOC=spin–orbit coupling.</abstract><cop>Germany</cop><pub>Blackwell Publishing Ltd</pub><pmid>27510509</pmid><doi>10.1002/anie.201606001</doi><tpages>4</tpages><edition>International ed. in English</edition><orcidid>https://orcid.org/0000-0001-8735-4933</orcidid><orcidid>https://orcid.org/0000-0003-1006-8482</orcidid><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1433-7851 |
| ispartof | Angewandte Chemie International Edition, 2016-09, Vol.55 (38), p.11503-11506 |
| issn | 1433-7851 1521-3773 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1817559693 |
| source | Wiley Online Library Journals Frontfile Complete |
| subjects | Chemical bonds Cobalt computational chemistry Corrinoids Crystal structure density functional calculations enzyme catalysis Mercury Methylation Reaction mechanisms Relativism Relativistic effects Relativity Spin-orbit interactions transition states |
| title | Mercury Methylation by Cobalt Corrinoids: Relativistic Effects Dictate the Reaction Mechanism |
| url | https://sfx.bib-bvb.de/sfx_tum?ctx_ver=Z39.88-2004&ctx_enc=info:ofi/enc:UTF-8&ctx_tim=2025-01-21T19%3A25%3A30IST&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=Mercury%20Methylation%20by%20Cobalt%20Corrinoids:%20Relativistic%20Effects%20Dictate%20the%20Reaction%20Mechanism&rft.jtitle=Angewandte%20Chemie%20International%20Edition&rft.au=Demissie,%20Taye%20B.&rft.date=2016-09-12&rft.volume=55&rft.issue=38&rft.spage=11503&rft.epage=11506&rft.pages=11503-11506&rft.issn=1433-7851&rft.eissn=1521-3773&rft.coden=ACIEAY&rft_id=info:doi/10.1002/anie.201606001&rft_dat=%3Cproquest_cross%3E1908276054%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=1816799376&rft_id=info:pmid/27510509&rfr_iscdi=true |