Manganese() Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate
A series of new manganese( ii ) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl) 2 ] ( 1 ), [Mn(CyHex-Salicyl) 2 ] ( 2 ), and [Mn(CyHe...
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| Veröffentlicht in: | New journal of chemistry 2021-06, Vol.45 (22), p.119-1117 |
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| container_title | New journal of chemistry |
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| creator | Hashimoto, Patricia K Oliveira, Larissa F Riga-Rocha, Beatriz A Machado, Antonio E. H Santana, Vinicius T Nascimento, Otaciro R Carvalho-Jr, Valdemiro P Goi, Beatriz E |
| description | A series of new manganese(
ii
) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)
2
] (
1
), [Mn(CyHex-Salicyl)
2
] (
2
), and [Mn(CyHep-Salicyl)
2
] (
3
). The complexes
1-3
were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(
ii
) complexes (
1
-
3
) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing Δ
G
values for the formation of dormant species.
The manganese Schiff-base complexes were applied in the OMRP of vinyl acetate. |
| doi_str_mv | 10.1039/d1nj00493j |
| format | Article |
| fullrecord | <record><control><sourceid>proquest_cross</sourceid><recordid>TN_cdi_proquest_journals_2537648134</recordid><sourceformat>XML</sourceformat><sourcesystem>PC</sourcesystem><sourcerecordid>2537648134</sourcerecordid><originalsourceid>FETCH-LOGICAL-c196t-d1bc3bc7898becaa278883d546a2f77b8011b7c65bb61fa38b4ed424f15c6f023</originalsourceid><addsrcrecordid>eNpF0D1PwzAQBmALgUQpLOxIkVgAKZCLHccZUfmsCgzAHNnOGVzSuNhppfLrcSmC6W549N7pJeQQsnPIaHXRQDfNMlbR6RYZAOVVWuUctuMOjKVZwfgu2QshGoCSw4B8PMjuTXYY8OQ0edbv1phUyYDpDBsre2wSj0v0waoWkwal7u1S9tZ1iXZd713brolsrJZtMnftaobefm2EM8nSdqs2kRr7mLVPdoxsAx78ziF5vbl-Gd2lk6fb-9HlJNVQ8T5tQGmqdCkqoVBLmZdCCNrE32VuylKJ-LsqNS-U4mAkFYphw3JmoNDcZDkdkuNN7ty7zwWGvp66he_iyTovaMmZAMqiOtso7V0IHk0993Ym_aqGrF6XWV_B4_inzHHERxvsg_5z_2XTbzYCcvk</addsrcrecordid><sourcetype>Aggregation Database</sourcetype><iscdi>true</iscdi><recordtype>article</recordtype><pqid>2537648134</pqid></control><display><type>article</type><title>Manganese() Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate</title><source>Royal Society Of Chemistry Journals 2008-</source><source>Alma/SFX Local Collection</source><creator>Hashimoto, Patricia K ; Oliveira, Larissa F ; Riga-Rocha, Beatriz A ; Machado, Antonio E. H ; Santana, Vinicius T ; Nascimento, Otaciro R ; Carvalho-Jr, Valdemiro P ; Goi, Beatriz E</creator><creatorcontrib>Hashimoto, Patricia K ; Oliveira, Larissa F ; Riga-Rocha, Beatriz A ; Machado, Antonio E. H ; Santana, Vinicius T ; Nascimento, Otaciro R ; Carvalho-Jr, Valdemiro P ; Goi, Beatriz E</creatorcontrib><description>A series of new manganese(
ii
) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)
2
] (
1
), [Mn(CyHex-Salicyl)
2
] (
2
), and [Mn(CyHep-Salicyl)
2
] (
3
). The complexes
1-3
were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(
ii
) complexes (
1
-
3
) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing Δ
G
values for the formation of dormant species.
The manganese Schiff-base complexes were applied in the OMRP of vinyl acetate.</description><identifier>ISSN: 1144-0546</identifier><identifier>EISSN: 1369-9261</identifier><identifier>DOI: 10.1039/d1nj00493j</identifier><language>eng</language><publisher>Cambridge: Royal Society of Chemistry</publisher><subject>Chemical analysis ; Degree of polymerization ; Imines ; Ligands ; Manganese ; Mathematical analysis ; Polymerization ; Steric hindrance ; Vinyl acetate</subject><ispartof>New journal of chemistry, 2021-06, Vol.45 (22), p.119-1117</ispartof><rights>Copyright Royal Society of Chemistry 2021</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c196t-d1bc3bc7898becaa278883d546a2f77b8011b7c65bb61fa38b4ed424f15c6f023</citedby><cites>FETCH-LOGICAL-c196t-d1bc3bc7898becaa278883d546a2f77b8011b7c65bb61fa38b4ed424f15c6f023</cites><orcidid>0000-0003-4369-7824 ; 0000-0001-8843-2841 ; 0000-0001-8149-3799</orcidid></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>Hashimoto, Patricia K</creatorcontrib><creatorcontrib>Oliveira, Larissa F</creatorcontrib><creatorcontrib>Riga-Rocha, Beatriz A</creatorcontrib><creatorcontrib>Machado, Antonio E. H</creatorcontrib><creatorcontrib>Santana, Vinicius T</creatorcontrib><creatorcontrib>Nascimento, Otaciro R</creatorcontrib><creatorcontrib>Carvalho-Jr, Valdemiro P</creatorcontrib><creatorcontrib>Goi, Beatriz E</creatorcontrib><title>Manganese() Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate</title><title>New journal of chemistry</title><description>A series of new manganese(
ii
) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)
2
] (
1
), [Mn(CyHex-Salicyl)
2
] (
2
), and [Mn(CyHep-Salicyl)
2
] (
3
). The complexes
1-3
were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(
ii
) complexes (
1
-
3
) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing Δ
G
values for the formation of dormant species.
The manganese Schiff-base complexes were applied in the OMRP of vinyl acetate.</description><subject>Chemical analysis</subject><subject>Degree of polymerization</subject><subject>Imines</subject><subject>Ligands</subject><subject>Manganese</subject><subject>Mathematical analysis</subject><subject>Polymerization</subject><subject>Steric hindrance</subject><subject>Vinyl acetate</subject><issn>1144-0546</issn><issn>1369-9261</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2021</creationdate><recordtype>article</recordtype><recordid>eNpF0D1PwzAQBmALgUQpLOxIkVgAKZCLHccZUfmsCgzAHNnOGVzSuNhppfLrcSmC6W549N7pJeQQsnPIaHXRQDfNMlbR6RYZAOVVWuUctuMOjKVZwfgu2QshGoCSw4B8PMjuTXYY8OQ0edbv1phUyYDpDBsre2wSj0v0waoWkwal7u1S9tZ1iXZd713brolsrJZtMnftaobefm2EM8nSdqs2kRr7mLVPdoxsAx78ziF5vbl-Gd2lk6fb-9HlJNVQ8T5tQGmqdCkqoVBLmZdCCNrE32VuylKJ-LsqNS-U4mAkFYphw3JmoNDcZDkdkuNN7ty7zwWGvp66he_iyTovaMmZAMqiOtso7V0IHk0993Ym_aqGrF6XWV_B4_inzHHERxvsg_5z_2XTbzYCcvk</recordid><startdate>20210607</startdate><enddate>20210607</enddate><creator>Hashimoto, Patricia K</creator><creator>Oliveira, Larissa F</creator><creator>Riga-Rocha, Beatriz A</creator><creator>Machado, Antonio E. H</creator><creator>Santana, Vinicius T</creator><creator>Nascimento, Otaciro R</creator><creator>Carvalho-Jr, Valdemiro P</creator><creator>Goi, Beatriz E</creator><general>Royal Society of Chemistry</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7SR</scope><scope>8BQ</scope><scope>8FD</scope><scope>H9R</scope><scope>JG9</scope><scope>KA0</scope><orcidid>https://orcid.org/0000-0003-4369-7824</orcidid><orcidid>https://orcid.org/0000-0001-8843-2841</orcidid><orcidid>https://orcid.org/0000-0001-8149-3799</orcidid></search><sort><creationdate>20210607</creationdate><title>Manganese() Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate</title><author>Hashimoto, Patricia K ; Oliveira, Larissa F ; Riga-Rocha, Beatriz A ; Machado, Antonio E. H ; Santana, Vinicius T ; Nascimento, Otaciro R ; Carvalho-Jr, Valdemiro P ; Goi, Beatriz E</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c196t-d1bc3bc7898becaa278883d546a2f77b8011b7c65bb61fa38b4ed424f15c6f023</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2021</creationdate><topic>Chemical analysis</topic><topic>Degree of polymerization</topic><topic>Imines</topic><topic>Ligands</topic><topic>Manganese</topic><topic>Mathematical analysis</topic><topic>Polymerization</topic><topic>Steric hindrance</topic><topic>Vinyl acetate</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Hashimoto, Patricia K</creatorcontrib><creatorcontrib>Oliveira, Larissa F</creatorcontrib><creatorcontrib>Riga-Rocha, Beatriz A</creatorcontrib><creatorcontrib>Machado, Antonio E. H</creatorcontrib><creatorcontrib>Santana, Vinicius T</creatorcontrib><creatorcontrib>Nascimento, Otaciro R</creatorcontrib><creatorcontrib>Carvalho-Jr, Valdemiro P</creatorcontrib><creatorcontrib>Goi, Beatriz E</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Illustrata: Natural Sciences</collection><collection>Materials Research Database</collection><collection>ProQuest Illustrata: Technology Collection</collection><jtitle>New journal of chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Hashimoto, Patricia K</au><au>Oliveira, Larissa F</au><au>Riga-Rocha, Beatriz A</au><au>Machado, Antonio E. H</au><au>Santana, Vinicius T</au><au>Nascimento, Otaciro R</au><au>Carvalho-Jr, Valdemiro P</au><au>Goi, Beatriz E</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Manganese() Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate</atitle><jtitle>New journal of chemistry</jtitle><date>2021-06-07</date><risdate>2021</risdate><volume>45</volume><issue>22</issue><spage>119</spage><epage>1117</epage><pages>119-1117</pages><issn>1144-0546</issn><eissn>1369-9261</eissn><abstract>A series of new manganese(
ii
) complexes were prepared with three bidentate Schiff-base ligands derived by condensation of salicylaldehyde and different cycloalkylamines (cycloalkyl = cyclopentyl, cyclohexyl, and cycloheptyl): [Mn(CyPen-Salicyl)
2
] (
1
), [Mn(CyHex-Salicyl)
2
] (
2
), and [Mn(CyHep-Salicyl)
2
] (
3
). The complexes
1-3
were characterized by FTIR, UV-vis and EPR spectroscopy, elemental analysis, cyclic voltammetry, and computational methods. The manganese(
ii
) complexes (
1
-
3
) were used as controlling agents for the polymerization of vinyl acetate (VAc) initiated by AIBN according to an organometallic-mediated radical polymerization (OMRP) mechanism. The VAc polymerization mediated by the Mn complexes suggests that the control level can be slightly tuned through substitution of the cycloalkyl group on the Schiff-base ligand. Kinetics studies and computational investigations support an RT mechanism and a tailorable Mn complex reactivity mainly altered by steric factors of the Schiff-base ligands. The calculated thermodynamic parameters agree with the mediating ability of these complexes, since the degree of polymerization control decreases with increasing steric hindrance of the Schiff-base ligands, as well as with increasing Δ
G
values for the formation of dormant species.
The manganese Schiff-base complexes were applied in the OMRP of vinyl acetate.</abstract><cop>Cambridge</cop><pub>Royal Society of Chemistry</pub><doi>10.1039/d1nj00493j</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0003-4369-7824</orcidid><orcidid>https://orcid.org/0000-0001-8843-2841</orcidid><orcidid>https://orcid.org/0000-0001-8149-3799</orcidid></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1144-0546 |
| ispartof | New journal of chemistry, 2021-06, Vol.45 (22), p.119-1117 |
| issn | 1144-0546 1369-9261 |
| language | eng |
| recordid | cdi_proquest_journals_2537648134 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Chemical analysis Degree of polymerization Imines Ligands Manganese Mathematical analysis Polymerization Steric hindrance Vinyl acetate |
| title | Manganese() Schiff-base-mediated reversible deactivation controlled radical polymerization of vinyl acetate |
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