Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability
Two neutral ligands, carbonyl (CO) and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes (CpFeBr(CO)(PR 3 ); Cp=C 5 H 5 ; PR 3 =PPh 3 , P(OPh) 3 , PMePh 2 , PMe 2 Ph, P( n -Bu) 3 ) for more active and versatile systems in transition metal-catalyzed living radical po...
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| Veröffentlicht in: | Polymer journal 2010-01, Vol.42 (1), p.17-24 |
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| creator | Ishio, Muneki Terashima, Takaya Ouchi, Makoto Sawamoto, Mitsuo |
| description | Two neutral ligands, carbonyl (CO) and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes (CpFeBr(CO)(PR
3
); Cp=C
5
H
5
; PR
3
=PPh
3
, P(OPh)
3
, PMePh
2
, PMe
2
Ph, P(
n
-Bu)
3
) for more active and versatile systems in transition metal-catalyzed living radical polymerization. For methyl methacrylate (MMA) with a bromide initiator [Me
2
C(CO
2
Me)CH
2
C(Me)-(CO
2
Me)Br; Me=CH
3
] [H-(MMA)
2
-Br], these hetero-ligated catalysts are superior, in terms of catalytic activity and molecular weight control, to similar homo-ligated half-metallocenes carrying two identical ligands such as CpFeBr(CO)
2
and CpFeBr(PR
3
)
2
. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability (>90% conversion within 24 h;
M
w
/
M
n
=1.29), and the ‘living’ character of the polymerizations therewith was proved by sequential monomer addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use. The concomitant high activity and high stability were attributed to the
in situ
generation of a real active catalyst with a 16-electron configuration by the irreversible release of the CO group from CpFeBr(CO)(PR
3
) on the activation of a terminal C–Br bond, as confirmed by the Fourier transform infrared monitoring of model reactions with the initiator as a dormant-end model compound.
Two neutral ligands, carbonyl and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes [CpFeBr(CO)(PR
3
)] for more active and versatile systems in transition metal-catalyzed living radical polymerization. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability, and the ‘living’ character of the polymerizations therewith was proved by sequential monomer-addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use. |
| doi_str_mv | 10.1038/pj.2009.315 |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_miscellaneous_1671341631</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2722268631</sourcerecordid><originalsourceid>FETCH-LOGICAL-c471t-8941b68d9355399dfa9c29e16e1481d7742a62c22952dc62f11a60a99b69cf8f3</originalsourceid><addsrcrecordid>eNpl0c1q3DAQAGARGuh221NfQJBLSuqNfmytlVtY-rOwkEt6NmNZXmuRJUfSFpxXyEtHy-YQ2tMwMx_DMIPQV0pWlPD6djqsGCFyxWl1gRaUl7IgVUk-oAUhnBW8luIj-hTjgRAmKlIu0MsGQuvdbItp8HEajNN40EkHX1izh6Q7PIDti1EnsNYrnfsmeHe93X7DCnJxjini3gdszV_j9jhAZxRYPHk7jzqYZ0jGuzusvFN-NAlcwqBSxmnG4DocE7TG5uwzuuzBRv3lLS7Rn58_Hje_i93Dr-3mfleock1TUcuStqLuJK8qLmXXg1RMaio0LWvardclA8EUY7JinRKspxQEASlbIVVf93yJrs9zp-CfjjqmZjRRaWvBaX-MDRXrfDoqOM306h968Mfg8nZNPjghNRVUZnVzVir4GIPumymYEcKc0cnVzXRoTo9p8mOy_n7WMSu31-H9zP_5KwTOkSw</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>1030081619</pqid></control><display><type>article</type><title>Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability</title><source>Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals</source><source>Alma/SFX Local Collection</source><creator>Ishio, Muneki ; Terashima, Takaya ; Ouchi, Makoto ; Sawamoto, Mitsuo</creator><creatorcontrib>Ishio, Muneki ; Terashima, Takaya ; Ouchi, Makoto ; Sawamoto, Mitsuo</creatorcontrib><description>Two neutral ligands, carbonyl (CO) and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes (CpFeBr(CO)(PR
3
); Cp=C
5
H
5
; PR
3
=PPh
3
, P(OPh)
3
, PMePh
2
, PMe
2
Ph, P(
n
-Bu)
3
) for more active and versatile systems in transition metal-catalyzed living radical polymerization. For methyl methacrylate (MMA) with a bromide initiator [Me
2
C(CO
2
Me)CH
2
C(Me)-(CO
2
Me)Br; Me=CH
3
] [H-(MMA)
2
-Br], these hetero-ligated catalysts are superior, in terms of catalytic activity and molecular weight control, to similar homo-ligated half-metallocenes carrying two identical ligands such as CpFeBr(CO)
2
and CpFeBr(PR
3
)
2
. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability (>90% conversion within 24 h;
M
w
/
M
n
=1.29), and the ‘living’ character of the polymerizations therewith was proved by sequential monomer addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use. The concomitant high activity and high stability were attributed to the
in situ
generation of a real active catalyst with a 16-electron configuration by the irreversible release of the CO group from CpFeBr(CO)(PR
3
) on the activation of a terminal C–Br bond, as confirmed by the Fourier transform infrared monitoring of model reactions with the initiator as a dormant-end model compound.
Two neutral ligands, carbonyl and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes [CpFeBr(CO)(PR
3
)] for more active and versatile systems in transition metal-catalyzed living radical polymerization. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability, and the ‘living’ character of the polymerizations therewith was proved by sequential monomer-addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use.</description><identifier>ISSN: 0032-3896</identifier><identifier>EISSN: 1349-0540</identifier><identifier>DOI: 10.1038/pj.2009.315</identifier><language>eng</language><publisher>London: Nature Publishing Group UK</publisher><subject>639/638/406/941 ; Biomaterials ; Bioorganic Chemistry ; Carbonyls ; Catalysis ; Catalysts ; Chemistry ; Chemistry and Materials Science ; Chemistry/Food Science ; invited-article ; Ligands ; Polymer Sciences ; Polymerization ; Polymethyl methacrylates ; Radicals ; Stability ; Surfaces and Interfaces ; Thin Films</subject><ispartof>Polymer journal, 2010-01, Vol.42 (1), p.17-24</ispartof><rights>The society of Polymer Science, Japan 2010</rights><rights>Copyright Nature Publishing Group Jan 2010</rights><lds50>peer_reviewed</lds50><oa>free_for_read</oa><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c471t-8941b68d9355399dfa9c29e16e1481d7742a62c22952dc62f11a60a99b69cf8f3</citedby><cites>FETCH-LOGICAL-c471t-8941b68d9355399dfa9c29e16e1481d7742a62c22952dc62f11a60a99b69cf8f3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27901,27902</link.rule.ids></links><search><creatorcontrib>Ishio, Muneki</creatorcontrib><creatorcontrib>Terashima, Takaya</creatorcontrib><creatorcontrib>Ouchi, Makoto</creatorcontrib><creatorcontrib>Sawamoto, Mitsuo</creatorcontrib><title>Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability</title><title>Polymer journal</title><addtitle>Polym J</addtitle><description>Two neutral ligands, carbonyl (CO) and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes (CpFeBr(CO)(PR
3
); Cp=C
5
H
5
; PR
3
=PPh
3
, P(OPh)
3
, PMePh
2
, PMe
2
Ph, P(
n
-Bu)
3
) for more active and versatile systems in transition metal-catalyzed living radical polymerization. For methyl methacrylate (MMA) with a bromide initiator [Me
2
C(CO
2
Me)CH
2
C(Me)-(CO
2
Me)Br; Me=CH
3
] [H-(MMA)
2
-Br], these hetero-ligated catalysts are superior, in terms of catalytic activity and molecular weight control, to similar homo-ligated half-metallocenes carrying two identical ligands such as CpFeBr(CO)
2
and CpFeBr(PR
3
)
2
. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability (>90% conversion within 24 h;
M
w
/
M
n
=1.29), and the ‘living’ character of the polymerizations therewith was proved by sequential monomer addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use. The concomitant high activity and high stability were attributed to the
in situ
generation of a real active catalyst with a 16-electron configuration by the irreversible release of the CO group from CpFeBr(CO)(PR
3
) on the activation of a terminal C–Br bond, as confirmed by the Fourier transform infrared monitoring of model reactions with the initiator as a dormant-end model compound.
Two neutral ligands, carbonyl and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes [CpFeBr(CO)(PR
3
)] for more active and versatile systems in transition metal-catalyzed living radical polymerization. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability, and the ‘living’ character of the polymerizations therewith was proved by sequential monomer-addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use.</description><subject>639/638/406/941</subject><subject>Biomaterials</subject><subject>Bioorganic Chemistry</subject><subject>Carbonyls</subject><subject>Catalysis</subject><subject>Catalysts</subject><subject>Chemistry</subject><subject>Chemistry and Materials Science</subject><subject>Chemistry/Food Science</subject><subject>invited-article</subject><subject>Ligands</subject><subject>Polymer Sciences</subject><subject>Polymerization</subject><subject>Polymethyl methacrylates</subject><subject>Radicals</subject><subject>Stability</subject><subject>Surfaces and Interfaces</subject><subject>Thin Films</subject><issn>0032-3896</issn><issn>1349-0540</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2010</creationdate><recordtype>article</recordtype><sourceid>BENPR</sourceid><recordid>eNpl0c1q3DAQAGARGuh221NfQJBLSuqNfmytlVtY-rOwkEt6NmNZXmuRJUfSFpxXyEtHy-YQ2tMwMx_DMIPQV0pWlPD6djqsGCFyxWl1gRaUl7IgVUk-oAUhnBW8luIj-hTjgRAmKlIu0MsGQuvdbItp8HEajNN40EkHX1izh6Q7PIDti1EnsNYrnfsmeHe93X7DCnJxjini3gdszV_j9jhAZxRYPHk7jzqYZ0jGuzusvFN-NAlcwqBSxmnG4DocE7TG5uwzuuzBRv3lLS7Rn58_Hje_i93Dr-3mfleock1TUcuStqLuJK8qLmXXg1RMaio0LWvardclA8EUY7JinRKspxQEASlbIVVf93yJrs9zp-CfjjqmZjRRaWvBaX-MDRXrfDoqOM306h968Mfg8nZNPjghNRVUZnVzVir4GIPumymYEcKc0cnVzXRoTo9p8mOy_n7WMSu31-H9zP_5KwTOkSw</recordid><startdate>20100101</startdate><enddate>20100101</enddate><creator>Ishio, Muneki</creator><creator>Terashima, Takaya</creator><creator>Ouchi, Makoto</creator><creator>Sawamoto, Mitsuo</creator><general>Nature Publishing Group UK</general><general>Nature Publishing Group</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8FD</scope><scope>8FE</scope><scope>8FG</scope><scope>ABJCF</scope><scope>AFKRA</scope><scope>BENPR</scope><scope>BGLVJ</scope><scope>CCPQU</scope><scope>D1I</scope><scope>DWQXO</scope><scope>HCIFZ</scope><scope>JG9</scope><scope>KB.</scope><scope>PDBOC</scope><scope>PQEST</scope><scope>PQQKQ</scope><scope>PQUKI</scope></search><sort><creationdate>20100101</creationdate><title>Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability</title><author>Ishio, Muneki ; Terashima, Takaya ; Ouchi, Makoto ; Sawamoto, Mitsuo</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c471t-8941b68d9355399dfa9c29e16e1481d7742a62c22952dc62f11a60a99b69cf8f3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2010</creationdate><topic>639/638/406/941</topic><topic>Biomaterials</topic><topic>Bioorganic Chemistry</topic><topic>Carbonyls</topic><topic>Catalysis</topic><topic>Catalysts</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Chemistry/Food Science</topic><topic>invited-article</topic><topic>Ligands</topic><topic>Polymer Sciences</topic><topic>Polymerization</topic><topic>Polymethyl methacrylates</topic><topic>Radicals</topic><topic>Stability</topic><topic>Surfaces and Interfaces</topic><topic>Thin Films</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ishio, Muneki</creatorcontrib><creatorcontrib>Terashima, Takaya</creatorcontrib><creatorcontrib>Ouchi, Makoto</creatorcontrib><creatorcontrib>Sawamoto, Mitsuo</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>Materials Science & Engineering Collection</collection><collection>ProQuest Central UK/Ireland</collection><collection>ProQuest Central</collection><collection>Technology Collection</collection><collection>ProQuest One Community College</collection><collection>ProQuest Materials Science Collection</collection><collection>ProQuest Central Korea</collection><collection>SciTech Premium Collection</collection><collection>Materials Research Database</collection><collection>Materials Science Database</collection><collection>Materials Science Collection</collection><collection>ProQuest One Academic Eastern Edition (DO NOT USE)</collection><collection>ProQuest One Academic</collection><collection>ProQuest One Academic UKI Edition</collection><jtitle>Polymer journal</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ishio, Muneki</au><au>Terashima, Takaya</au><au>Ouchi, Makoto</au><au>Sawamoto, Mitsuo</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability</atitle><jtitle>Polymer journal</jtitle><stitle>Polym J</stitle><date>2010-01-01</date><risdate>2010</risdate><volume>42</volume><issue>1</issue><spage>17</spage><epage>24</epage><pages>17-24</pages><issn>0032-3896</issn><eissn>1349-0540</eissn><abstract>Two neutral ligands, carbonyl (CO) and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes (CpFeBr(CO)(PR
3
); Cp=C
5
H
5
; PR
3
=PPh
3
, P(OPh)
3
, PMePh
2
, PMe
2
Ph, P(
n
-Bu)
3
) for more active and versatile systems in transition metal-catalyzed living radical polymerization. For methyl methacrylate (MMA) with a bromide initiator [Me
2
C(CO
2
Me)CH
2
C(Me)-(CO
2
Me)Br; Me=CH
3
] [H-(MMA)
2
-Br], these hetero-ligated catalysts are superior, in terms of catalytic activity and molecular weight control, to similar homo-ligated half-metallocenes carrying two identical ligands such as CpFeBr(CO)
2
and CpFeBr(PR
3
)
2
. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability (>90% conversion within 24 h;
M
w
/
M
n
=1.29), and the ‘living’ character of the polymerizations therewith was proved by sequential monomer addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use. The concomitant high activity and high stability were attributed to the
in situ
generation of a real active catalyst with a 16-electron configuration by the irreversible release of the CO group from CpFeBr(CO)(PR
3
) on the activation of a terminal C–Br bond, as confirmed by the Fourier transform infrared monitoring of model reactions with the initiator as a dormant-end model compound.
Two neutral ligands, carbonyl and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes [CpFeBr(CO)(PR
3
)] for more active and versatile systems in transition metal-catalyzed living radical polymerization. Among the CpFeBr(CO)(PR
3
) complexes examined, CpFeBr(CO)(PMePh
2
) showed the highest activity and the best controllability, and the ‘living’ character of the polymerizations therewith was proved by sequential monomer-addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use.</abstract><cop>London</cop><pub>Nature Publishing Group UK</pub><doi>10.1038/pj.2009.315</doi><tpages>8</tpages><oa>free_for_read</oa></addata></record> |
| fulltext | fulltext |
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| ispartof | Polymer journal, 2010-01, Vol.42 (1), p.17-24 |
| issn | 0032-3896 1349-0540 |
| language | eng |
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| source | Elektronische Zeitschriftenbibliothek - Frei zugängliche E-Journals; Alma/SFX Local Collection |
| subjects | 639/638/406/941 Biomaterials Bioorganic Chemistry Carbonyls Catalysis Catalysts Chemistry Chemistry and Materials Science Chemistry/Food Science invited-article Ligands Polymer Sciences Polymerization Polymethyl methacrylates Radicals Stability Surfaces and Interfaces Thin Films |
| title | Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability |
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