Atom-Transfer Radical Addition Reactions Catalyzed by RuCp Complexes: A Mechanistic Study
Kinetic and spectroscopic analyses were performed to gain information about the mechanism of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl), in the presence and in the absence of the reducing agent magnesium. The rea...
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| Veröffentlicht in: | Chemistry : a European journal 2009-11, Vol.15 (43), p.11601-11607 |
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| container_title | Chemistry : a European journal |
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| creator | Fernández-Zúmel, Mariano A. Thommes, Katrin Kiefer, Gregor Sienkiewicz, Andrzej Pierzchala, Katarzyna Severin, Kay |
| description | Kinetic and spectroscopic analyses were performed to gain information about the mechanism of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl), in the presence and in the absence of the reducing agent magnesium. The reactions of styrene with ethyl trichloroacetate, ethyl dichloroacetate, or dichloroacetonitrile were used as test reactions. The results show that for substrates with high intrinsic reactivity, such as ethyl trichloroacetate, the oxidation state of the catalyst in the resting state is +3, and that the reaction is zero‐order with respect to the halogenated compound. Furthermore, the kinetic data suggest that the metal catalyst is not directly involved in the rate‐limiting step of the reaction.
Radical reactions: Kinetic and spectroscopic analyses provide information about the mechanism (see figure) of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl). |
| doi_str_mv | 10.1002/chem.200901396 |
| format | Article |
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Radical reactions: Kinetic and spectroscopic analyses provide information about the mechanism (see figure) of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl).</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.200901396</identifier><identifier>PMID: 19750528</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>atom transfer ; homogeneous catalysis ; kinetics ; radical reactions ; ruthenium</subject><ispartof>Chemistry : a European journal, 2009-11, Vol.15 (43), p.11601-11607</ispartof><rights>Copyright © 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c4486-46c84190067f1da8ee10b457693169f08ea3ebad6846e59795fa6ebe1676c9b63</citedby><cites>FETCH-LOGICAL-c4486-46c84190067f1da8ee10b457693169f08ea3ebad6846e59795fa6ebe1676c9b63</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><linktopdf>$$Uhttps://onlinelibrary.wiley.com/doi/pdf/10.1002%2Fchem.200901396$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.200901396$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1417,27924,27925,45574,45575</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/19750528$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Fernández-Zúmel, Mariano A.</creatorcontrib><creatorcontrib>Thommes, Katrin</creatorcontrib><creatorcontrib>Kiefer, Gregor</creatorcontrib><creatorcontrib>Sienkiewicz, Andrzej</creatorcontrib><creatorcontrib>Pierzchala, Katarzyna</creatorcontrib><creatorcontrib>Severin, Kay</creatorcontrib><title>Atom-Transfer Radical Addition Reactions Catalyzed by RuCp Complexes: A Mechanistic Study</title><title>Chemistry : a European journal</title><addtitle>Chem. Eur. J</addtitle><description>Kinetic and spectroscopic analyses were performed to gain information about the mechanism of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl), in the presence and in the absence of the reducing agent magnesium. The reactions of styrene with ethyl trichloroacetate, ethyl dichloroacetate, or dichloroacetonitrile were used as test reactions. The results show that for substrates with high intrinsic reactivity, such as ethyl trichloroacetate, the oxidation state of the catalyst in the resting state is +3, and that the reaction is zero‐order with respect to the halogenated compound. Furthermore, the kinetic data suggest that the metal catalyst is not directly involved in the rate‐limiting step of the reaction.
Radical reactions: Kinetic and spectroscopic analyses provide information about the mechanism (see figure) of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl).</description><subject>atom transfer</subject><subject>homogeneous catalysis</subject><subject>kinetics</subject><subject>radical reactions</subject><subject>ruthenium</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2009</creationdate><recordtype>article</recordtype><recordid>eNqFkDtPwzAURi0EgvJYGZE3phQ7fsVsJYKC1AIqLzFZjnMjAklT4kQQfj2pWgEb073D-c5wEDqkZEgJCU_cC5TDkBBNKNNyAw2oCGnAlBSbaEA0V4EUTO-gXe9fSY9JxrbRDtVKEBFGA_Q8aqoyuK_t3GdQ45lNc2cLPErTvMmrOZ6BdcvH49g2tui-IMVJh2dtvMBxVS4K-AR_ikd4Cu7FznPf5A7fNW3a7aOtzBYeDtZ3Dz1cnN_Hl8HkZnwVjyaB4zySAZcu4lQTIlVGUxsBUJJwoaRmVOqMRGAZJDaVEZcgtNIisxISoFJJpxPJ9tDxyruoq_cWfGPK3DsoCjuHqvVGMU4p7yv05HBFurryvobMLOq8tHVnKDHLmmZZ0_zU7AdHa3WblJD-4ut8PaBXwEdeQPePzsSX59O_8mC17ZvB58_W1m9GKqaEeboem-kkjMbx45m5Zd-9Z4-k</recordid><startdate>20091102</startdate><enddate>20091102</enddate><creator>Fernández-Zúmel, Mariano A.</creator><creator>Thommes, Katrin</creator><creator>Kiefer, Gregor</creator><creator>Sienkiewicz, Andrzej</creator><creator>Pierzchala, Katarzyna</creator><creator>Severin, Kay</creator><general>WILEY-VCH Verlag</general><general>WILEY‐VCH Verlag</general><scope>BSCLL</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20091102</creationdate><title>Atom-Transfer Radical Addition Reactions Catalyzed by RuCp Complexes: A Mechanistic Study</title><author>Fernández-Zúmel, Mariano A. ; Thommes, Katrin ; Kiefer, Gregor ; Sienkiewicz, Andrzej ; Pierzchala, Katarzyna ; Severin, Kay</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c4486-46c84190067f1da8ee10b457693169f08ea3ebad6846e59795fa6ebe1676c9b63</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2009</creationdate><topic>atom transfer</topic><topic>homogeneous catalysis</topic><topic>kinetics</topic><topic>radical reactions</topic><topic>ruthenium</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Fernández-Zúmel, Mariano A.</creatorcontrib><creatorcontrib>Thommes, Katrin</creatorcontrib><creatorcontrib>Kiefer, Gregor</creatorcontrib><creatorcontrib>Sienkiewicz, Andrzej</creatorcontrib><creatorcontrib>Pierzchala, Katarzyna</creatorcontrib><creatorcontrib>Severin, Kay</creatorcontrib><collection>Istex</collection><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><jtitle>Chemistry : a European journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Fernández-Zúmel, Mariano A.</au><au>Thommes, Katrin</au><au>Kiefer, Gregor</au><au>Sienkiewicz, Andrzej</au><au>Pierzchala, Katarzyna</au><au>Severin, Kay</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Atom-Transfer Radical Addition Reactions Catalyzed by RuCp Complexes: A Mechanistic Study</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chem. Eur. J</addtitle><date>2009-11-02</date><risdate>2009</risdate><volume>15</volume><issue>43</issue><spage>11601</spage><epage>11607</epage><pages>11601-11607</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>Kinetic and spectroscopic analyses were performed to gain information about the mechanism of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl), in the presence and in the absence of the reducing agent magnesium. The reactions of styrene with ethyl trichloroacetate, ethyl dichloroacetate, or dichloroacetonitrile were used as test reactions. The results show that for substrates with high intrinsic reactivity, such as ethyl trichloroacetate, the oxidation state of the catalyst in the resting state is +3, and that the reaction is zero‐order with respect to the halogenated compound. Furthermore, the kinetic data suggest that the metal catalyst is not directly involved in the rate‐limiting step of the reaction.
Radical reactions: Kinetic and spectroscopic analyses provide information about the mechanism (see figure) of atom‐transfer radical reactions catalyzed by the complexes [RuCl2Cp*(PPh3)] and [RuClCp*(PPh3)2] (Cp*=pentamethylcyclopentadienyl).</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>19750528</pmid><doi>10.1002/chem.200901396</doi><tpages>7</tpages></addata></record> |
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| subjects | atom transfer homogeneous catalysis kinetics radical reactions ruthenium |
| title | Atom-Transfer Radical Addition Reactions Catalyzed by RuCp Complexes: A Mechanistic Study |
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