Unprecedented Polymerization of ε-Caprolactone Initiated by a Single-Site Lanthanide Borohydride Complex, [Sm(η-C5Me5)2(BH4)(thf)]: Mechanistic Insights
The monoborohydride lanthanide complex [Sm(Cp*)2(BH4)(thf)] (1 a) (Cp* = η‐C5Me5), has been successfully used for the controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL). The organometallic samarium(III) initiator 1 a produces, in quantitative yields, α,ω‐dihydroxytelechelic poly(ε‐capro...
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| Veröffentlicht in: | Chemistry : a European journal 2004-08, Vol.10 (16), p.4054-4062 |
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| creator | Palard, Isabelle Soum, Alain Guillaume, Sophie M. |
| description | The monoborohydride lanthanide complex [Sm(Cp*)2(BH4)(thf)] (1 a) (Cp* = η‐C5Me5), has been successfully used for the controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL). The organometallic samarium(III) initiator 1 a produces, in quantitative yields, α,ω‐dihydroxytelechelic poly(ε‐caprolactone) displaying relatively narrow polydispersity indices ( |
| doi_str_mv | 10.1002/chem.200400319 |
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Controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL) has been achieved by using [Sm(Cp*)2(BH4)(thf)] (1) (Cp* = η‐C5Me5). The single‐site initiator 1, which produces α,ω‐dihydroxytelechelic poly(ε‐caprolactone) displaying relatively narrow polydispersity indices (<1.3) within a short period of time (30 min), allows a better understanding of the polymerization mechanism.</description><identifier>ISSN: 0947-6539</identifier><identifier>EISSN: 1521-3765</identifier><identifier>DOI: 10.1002/chem.200400319</identifier><identifier>PMID: 15317053</identifier><language>eng</language><publisher>Weinheim: WILEY-VCH Verlag</publisher><subject>borohydride ; hydroxytelechelic ; lactones ; rare-earth metal ; ring-opening polymerization</subject><ispartof>Chemistry : a European journal, 2004-08, Vol.10 (16), p.4054-4062</ispartof><rights>Copyright © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3799-b904c2a93a94c623047a0c02f79873faaa0c2de34b4efc8fc0700011181465b83</citedby><cites>FETCH-LOGICAL-c3799-b904c2a93a94c623047a0c02f79873faaa0c2de34b4efc8fc0700011181465b83</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.200400319$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Fchem.200400319$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,780,784,1416,27922,27923,45572,45573</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/15317053$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Palard, Isabelle</creatorcontrib><creatorcontrib>Soum, Alain</creatorcontrib><creatorcontrib>Guillaume, Sophie M.</creatorcontrib><title>Unprecedented Polymerization of ε-Caprolactone Initiated by a Single-Site Lanthanide Borohydride Complex, [Sm(η-C5Me5)2(BH4)(thf)]: Mechanistic Insights</title><title>Chemistry : a European journal</title><addtitle>Chemistry - A European Journal</addtitle><description>The monoborohydride lanthanide complex [Sm(Cp*)2(BH4)(thf)] (1 a) (Cp* = η‐C5Me5), has been successfully used for the controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL). The organometallic samarium(III) initiator 1 a produces, in quantitative yields, α,ω‐dihydroxytelechelic poly(ε‐caprolactone) displaying relatively narrow polydispersity indices (<1.3) within a short period of time (30 min). The polymers have been characterized by 1H and 13C NMR, SEC, and MALDI‐TOF MS analyses. Use of the single‐site initiator 1 a allows a better understanding of the polymerization mechanism, in particular with the identification of the intermediate compound [Sm(Cp*)2(BH4)(ε‐CL)] (1 b). Indeed, one molecule of ε‐CL initially displaces the coordinated THF in 1 a to give 1 b. Then, ε‐CL opening (through cleavage of the cyclic ester oxygen–acyl bond) and insertion into the SmHBH3 bond followed by reduction of the carbonyl function by the BH3 end‐group ligand, leads to the samarium alkoxyborane derivative [Sm(Cp*)2{O(CH2)6O(BH2)}] (2). This compound subsequently initiates the polymerization of ε‐CL through a coordination–insertion mechanism. Finally, upon hydrolysis, α,ω‐dihydroxypoly(ε‐caprolactone), HO(CH2)5C(O){O(CH2)5C(O)}nO(CH2)6OH (4) is recovered. The stereoelectronic contribution of the two Cp* ligands appears to slow down the polymerization and to limit transesterification reactions.
Controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL) has been achieved by using [Sm(Cp*)2(BH4)(thf)] (1) (Cp* = η‐C5Me5). The single‐site initiator 1, which produces α,ω‐dihydroxytelechelic poly(ε‐caprolactone) displaying relatively narrow polydispersity indices (<1.3) within a short period of time (30 min), allows a better understanding of the polymerization mechanism.</description><subject>borohydride</subject><subject>hydroxytelechelic</subject><subject>lactones</subject><subject>rare-earth metal</subject><subject>ring-opening polymerization</subject><issn>0947-6539</issn><issn>1521-3765</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2004</creationdate><recordtype>article</recordtype><recordid>eNqFkdFu0zAUhi0EYmVwyyXKFWolUuzYiWvuaDTWSS1MdNMkELIc52T1SOJiu2LhUXgPxFvsmUjUanDH1fGRvv8_8v8j9JzgKcE4ea030EwTjBnGlIgHaETShMSUZ-lDNMKC8ThLqThCT7y_wRiLjNLH6IiklHCc0hH6edluHWgooQ1QRue27hpw5ocKxraRraK7X3Guts7WSgfbQnTWmmDUwBZdpKK1aa9riNcmQLRUbdio1pQQza2zm650wzu3zbaG21fR53Uzvvsd5-kK0kkyni_YZBw21eTLm2gFelD6YHR_wZvrTfBP0aNK1R6eHeYxunx3cpEv4uWH07P87TLWlAsRFwIznShBlWA6SyhmXGGNk4qLGaeVUv2WlEBZwaDSs0pj3gdBCJkRlqXFjB6jl3vf_pffduCDbIzXUNeqBbvzMsv6MyRjPTjdg9pZ7x1UcutMo1wnCZZDG3JoQ9630QteHJx3RQPlX_wQfw-IPfDd1ND9x07mi5PVv-bxXtunBrf3WuW-yoxTnsqr96fy4zmZfxLZhbyifwDpVqck</recordid><startdate>20040820</startdate><enddate>20040820</enddate><creator>Palard, Isabelle</creator><creator>Soum, Alain</creator><creator>Guillaume, Sophie M.</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>20040820</creationdate><title>Unprecedented Polymerization of ε-Caprolactone Initiated by a Single-Site Lanthanide Borohydride Complex, [Sm(η-C5Me5)2(BH4)(thf)]: Mechanistic Insights</title><author>Palard, Isabelle ; Soum, Alain ; Guillaume, Sophie M.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3799-b904c2a93a94c623047a0c02f79873faaa0c2de34b4efc8fc0700011181465b83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2004</creationdate><topic>borohydride</topic><topic>hydroxytelechelic</topic><topic>lactones</topic><topic>rare-earth metal</topic><topic>ring-opening polymerization</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Palard, Isabelle</creatorcontrib><creatorcontrib>Soum, Alain</creatorcontrib><creatorcontrib>Guillaume, Sophie M.</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>Palard, Isabelle</au><au>Soum, Alain</au><au>Guillaume, Sophie M.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Unprecedented Polymerization of ε-Caprolactone Initiated by a Single-Site Lanthanide Borohydride Complex, [Sm(η-C5Me5)2(BH4)(thf)]: Mechanistic Insights</atitle><jtitle>Chemistry : a European journal</jtitle><addtitle>Chemistry - A European Journal</addtitle><date>2004-08-20</date><risdate>2004</risdate><volume>10</volume><issue>16</issue><spage>4054</spage><epage>4062</epage><pages>4054-4062</pages><issn>0947-6539</issn><eissn>1521-3765</eissn><abstract>The monoborohydride lanthanide complex [Sm(Cp*)2(BH4)(thf)] (1 a) (Cp* = η‐C5Me5), has been successfully used for the controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL). The organometallic samarium(III) initiator 1 a produces, in quantitative yields, α,ω‐dihydroxytelechelic poly(ε‐caprolactone) displaying relatively narrow polydispersity indices (<1.3) within a short period of time (30 min). The polymers have been characterized by 1H and 13C NMR, SEC, and MALDI‐TOF MS analyses. Use of the single‐site initiator 1 a allows a better understanding of the polymerization mechanism, in particular with the identification of the intermediate compound [Sm(Cp*)2(BH4)(ε‐CL)] (1 b). Indeed, one molecule of ε‐CL initially displaces the coordinated THF in 1 a to give 1 b. Then, ε‐CL opening (through cleavage of the cyclic ester oxygen–acyl bond) and insertion into the SmHBH3 bond followed by reduction of the carbonyl function by the BH3 end‐group ligand, leads to the samarium alkoxyborane derivative [Sm(Cp*)2{O(CH2)6O(BH2)}] (2). This compound subsequently initiates the polymerization of ε‐CL through a coordination–insertion mechanism. Finally, upon hydrolysis, α,ω‐dihydroxypoly(ε‐caprolactone), HO(CH2)5C(O){O(CH2)5C(O)}nO(CH2)6OH (4) is recovered. The stereoelectronic contribution of the two Cp* ligands appears to slow down the polymerization and to limit transesterification reactions.
Controlled ring‐opening polymerization of ε‐caprolactone (ε‐CL) has been achieved by using [Sm(Cp*)2(BH4)(thf)] (1) (Cp* = η‐C5Me5). The single‐site initiator 1, which produces α,ω‐dihydroxytelechelic poly(ε‐caprolactone) displaying relatively narrow polydispersity indices (<1.3) within a short period of time (30 min), allows a better understanding of the polymerization mechanism.</abstract><cop>Weinheim</cop><pub>WILEY-VCH Verlag</pub><pmid>15317053</pmid><doi>10.1002/chem.200400319</doi><tpages>9</tpages></addata></record> |
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| subjects | borohydride hydroxytelechelic lactones rare-earth metal ring-opening polymerization |
| title | Unprecedented Polymerization of ε-Caprolactone Initiated by a Single-Site Lanthanide Borohydride Complex, [Sm(η-C5Me5)2(BH4)(thf)]: Mechanistic Insights |
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