Dual catalytic performance of arene‐ruthenium amine complexes for norbornene ring‐opening metathesis and methyl methacrylate atom‐transfer radical polymerizations
Arene ruthenium(II) complexes bearing the cyclic amines RuCl2(η6‐p‐cymene)(pyrrolidine)] (1), [RuCl2(η6‐p‐cymene)(piperidine)] (2), and [RuCl2(η6‐p‐cymene)(peridroazepine)] (3) were successfully synthesized. Complexes 1–3 were fully characterized by means of Fourier transform infrared, UV–visible, a...
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| Veröffentlicht in: | Applied organometallic chemistry 2020-05, Vol.34 (5), p.n/a |
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| creator | Cruz, Thais R. Silva, Eliada A. Oliveira, Douglas P. Martins, Daniele M. Gois, Patrik D.S. Machado, Antonio E.H. Maia, Pedro Ivo S. Goi, Beatriz E. Lima‐Neto, Benedito S. Carvalho‐Jr, Valdemiro P. |
| description | Arene ruthenium(II) complexes bearing the cyclic amines RuCl2(η6‐p‐cymene)(pyrrolidine)] (1), [RuCl2(η6‐p‐cymene)(piperidine)] (2), and [RuCl2(η6‐p‐cymene)(peridroazepine)] (3) were successfully synthesized. Complexes 1–3 were fully characterized by means of Fourier transform infrared, UV–visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X‐ray crystallography. These compounds were evaluated as catalytic precursors for ring‐opening metathesis polymerization (ROMP) of norbornene (NBE) and atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1–3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different [NBE]/[EDA]/[Ru] ratios, temperatures (25 and 50°C), and reaction times (5–60 min). The highest yields of polyNBE were obtained with [NBE]/[EDA]/[Ru] = 5000/28/1 for 60 min at 50°C. MMA polymerization via ATRP was conducted using 1–3 as catalysts in the presence of ethyl‐α‐bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 95°C. The increase in molecular weight as function of time indicates that complexes 1–3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP.
A series of [RuCl2(p‐cymene)(amine)] complexes, where amine is pyrrolidine (1), piperidine (2), or perhydroazepine (3), were synthesized. The ruthenium complexes (1–3) were fully characterized by elemental analysis, FT‐IR, UV–Vis, NMR, XRD, cyclic voltammetry and computational studies. Complexes 1–3 have been successfully employed as catalytic precursors for ROMP of norbornene and ATRP of methyl methacrylate. |
| doi_str_mv | 10.1002/aoc.5602 |
| format | Article |
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A series of [RuCl2(p‐cymene)(amine)] complexes, where amine is pyrrolidine (1), piperidine (2), or perhydroazepine (3), were synthesized. The ruthenium complexes (1–3) were fully characterized by elemental analysis, FT‐IR, UV–Vis, NMR, XRD, cyclic voltammetry and computational studies. Complexes 1–3 have been successfully employed as catalytic precursors for ROMP of norbornene and ATRP of methyl methacrylate.</description><identifier>ISSN: 0268-2605</identifier><identifier>EISSN: 1099-0739</identifier><identifier>DOI: 10.1002/aoc.5602</identifier><language>eng</language><publisher>Chichester: Wiley Subscription Services, Inc</publisher><subject>Amines ; ATRP ; Chemical analysis ; Chemistry ; Crystallography ; Decomposition reactions ; Fourier transforms ; Infrared analysis ; Metathesis ; NMR spectroscopy ; olefin ; Piperidine ; Polymerization ; Polymethyl methacrylate ; p‐cymene ; Reaction time ; ROMP ; Ruthenium ; Ruthenium compounds ; Single crystals</subject><ispartof>Applied organometallic chemistry, 2020-05, Vol.34 (5), p.n/a</ispartof><rights>2020 John Wiley & Sons, Ltd.</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c3302-309859a55651a20cdb445d12fdfa381a2a58651aea769982505f5f6f4bc6934a3</citedby><cites>FETCH-LOGICAL-c3302-309859a55651a20cdb445d12fdfa381a2a58651aea769982505f5f6f4bc6934a3</cites><orcidid>0000-0001-8843-2841 ; 0000-0003-4699-9481</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%2Faoc.5602$$EPDF$$P50$$Gwiley$$H</linktopdf><linktohtml>$$Uhttps://onlinelibrary.wiley.com/doi/full/10.1002%2Faoc.5602$$EHTML$$P50$$Gwiley$$H</linktohtml><link.rule.ids>314,776,780,1411,27901,27902,45550,45551</link.rule.ids></links><search><creatorcontrib>Cruz, Thais R.</creatorcontrib><creatorcontrib>Silva, Eliada A.</creatorcontrib><creatorcontrib>Oliveira, Douglas P.</creatorcontrib><creatorcontrib>Martins, Daniele M.</creatorcontrib><creatorcontrib>Gois, Patrik D.S.</creatorcontrib><creatorcontrib>Machado, Antonio E.H.</creatorcontrib><creatorcontrib>Maia, Pedro Ivo S.</creatorcontrib><creatorcontrib>Goi, Beatriz E.</creatorcontrib><creatorcontrib>Lima‐Neto, Benedito S.</creatorcontrib><creatorcontrib>Carvalho‐Jr, Valdemiro P.</creatorcontrib><title>Dual catalytic performance of arene‐ruthenium amine complexes for norbornene ring‐opening metathesis and methyl methacrylate atom‐transfer radical polymerizations</title><title>Applied organometallic chemistry</title><description>Arene ruthenium(II) complexes bearing the cyclic amines RuCl2(η6‐p‐cymene)(pyrrolidine)] (1), [RuCl2(η6‐p‐cymene)(piperidine)] (2), and [RuCl2(η6‐p‐cymene)(peridroazepine)] (3) were successfully synthesized. Complexes 1–3 were fully characterized by means of Fourier transform infrared, UV–visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X‐ray crystallography. These compounds were evaluated as catalytic precursors for ring‐opening metathesis polymerization (ROMP) of norbornene (NBE) and atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1–3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different [NBE]/[EDA]/[Ru] ratios, temperatures (25 and 50°C), and reaction times (5–60 min). The highest yields of polyNBE were obtained with [NBE]/[EDA]/[Ru] = 5000/28/1 for 60 min at 50°C. MMA polymerization via ATRP was conducted using 1–3 as catalysts in the presence of ethyl‐α‐bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 95°C. The increase in molecular weight as function of time indicates that complexes 1–3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP.
A series of [RuCl2(p‐cymene)(amine)] complexes, where amine is pyrrolidine (1), piperidine (2), or perhydroazepine (3), were synthesized. The ruthenium complexes (1–3) were fully characterized by elemental analysis, FT‐IR, UV–Vis, NMR, XRD, cyclic voltammetry and computational studies. Complexes 1–3 have been successfully employed as catalytic precursors for ROMP of norbornene and ATRP of methyl methacrylate.</description><subject>Amines</subject><subject>ATRP</subject><subject>Chemical analysis</subject><subject>Chemistry</subject><subject>Crystallography</subject><subject>Decomposition reactions</subject><subject>Fourier transforms</subject><subject>Infrared analysis</subject><subject>Metathesis</subject><subject>NMR spectroscopy</subject><subject>olefin</subject><subject>Piperidine</subject><subject>Polymerization</subject><subject>Polymethyl methacrylate</subject><subject>p‐cymene</subject><subject>Reaction time</subject><subject>ROMP</subject><subject>Ruthenium</subject><subject>Ruthenium compounds</subject><subject>Single crystals</subject><issn>0268-2605</issn><issn>1099-0739</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2020</creationdate><recordtype>article</recordtype><recordid>eNp10cFO3DAQBmCrAokFKvEIlnrpJeA4cTY-oqUFJCQu5RzNOmMwSux07IiGUx-hj9Hn4knqZbn24pHtb8aWfsbOSnFeCiEvIJhz1Qj5ia1KoXUh1pU-YCshm7aQjVBH7DjGZyGEbsp6xf5ezTBwAwmGJTnDJyQbaARvkAfLgdDj2-8_NKcn9G4eOYzOIzdhnAb8hZFnzX2gbSCfKSfnH7MPU9b-kY-YIHdGFzn4frd9Wob3AoaWARJySGHMHYnAR4vECXpn8p-mMCwjknuF5IKPp-zQwhDx80c9YQ_fv_3Y3BR399e3m8u7wlSVkEUldKs0KNWoEqQw_bauVV9K21uo2nwEqt1dIawbrVuphLLKNrbemkZXNVQn7Mt-7kTh54wxdc9hJp-f7GTVqnVeapXV170yFGIktN1EbgRaulJ0uxy6nEO3yyHTYk9f3IDLf113eb959_8ANWOQ2Q</recordid><startdate>202005</startdate><enddate>202005</enddate><creator>Cruz, Thais R.</creator><creator>Silva, Eliada A.</creator><creator>Oliveira, Douglas P.</creator><creator>Martins, Daniele M.</creator><creator>Gois, Patrik D.S.</creator><creator>Machado, Antonio E.H.</creator><creator>Maia, Pedro Ivo S.</creator><creator>Goi, Beatriz E.</creator><creator>Lima‐Neto, Benedito S.</creator><creator>Carvalho‐Jr, Valdemiro P.</creator><general>Wiley Subscription Services, Inc</general><scope>AAYXX</scope><scope>CITATION</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope><orcidid>https://orcid.org/0000-0001-8843-2841</orcidid><orcidid>https://orcid.org/0000-0003-4699-9481</orcidid></search><sort><creationdate>202005</creationdate><title>Dual catalytic performance of arene‐ruthenium amine complexes for norbornene ring‐opening metathesis and methyl methacrylate atom‐transfer radical polymerizations</title><author>Cruz, Thais R. ; Silva, Eliada A. ; Oliveira, Douglas P. ; Martins, Daniele M. ; Gois, Patrik D.S. ; Machado, Antonio E.H. ; Maia, Pedro Ivo S. ; Goi, Beatriz E. ; Lima‐Neto, Benedito S. ; Carvalho‐Jr, Valdemiro P.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c3302-309859a55651a20cdb445d12fdfa381a2a58651aea769982505f5f6f4bc6934a3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2020</creationdate><topic>Amines</topic><topic>ATRP</topic><topic>Chemical analysis</topic><topic>Chemistry</topic><topic>Crystallography</topic><topic>Decomposition reactions</topic><topic>Fourier transforms</topic><topic>Infrared analysis</topic><topic>Metathesis</topic><topic>NMR spectroscopy</topic><topic>olefin</topic><topic>Piperidine</topic><topic>Polymerization</topic><topic>Polymethyl methacrylate</topic><topic>p‐cymene</topic><topic>Reaction time</topic><topic>ROMP</topic><topic>Ruthenium</topic><topic>Ruthenium compounds</topic><topic>Single crystals</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Cruz, Thais R.</creatorcontrib><creatorcontrib>Silva, Eliada A.</creatorcontrib><creatorcontrib>Oliveira, Douglas P.</creatorcontrib><creatorcontrib>Martins, Daniele M.</creatorcontrib><creatorcontrib>Gois, Patrik D.S.</creatorcontrib><creatorcontrib>Machado, Antonio E.H.</creatorcontrib><creatorcontrib>Maia, Pedro Ivo S.</creatorcontrib><creatorcontrib>Goi, Beatriz E.</creatorcontrib><creatorcontrib>Lima‐Neto, Benedito S.</creatorcontrib><creatorcontrib>Carvalho‐Jr, Valdemiro P.</creatorcontrib><collection>CrossRef</collection><collection>Solid State and Superconductivity Abstracts</collection><collection>METADEX</collection><collection>Technology Research Database</collection><collection>Materials Research Database</collection><collection>Advanced Technologies Database with Aerospace</collection><jtitle>Applied organometallic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Cruz, Thais R.</au><au>Silva, Eliada A.</au><au>Oliveira, Douglas P.</au><au>Martins, Daniele M.</au><au>Gois, Patrik D.S.</au><au>Machado, Antonio E.H.</au><au>Maia, Pedro Ivo S.</au><au>Goi, Beatriz E.</au><au>Lima‐Neto, Benedito S.</au><au>Carvalho‐Jr, Valdemiro P.</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Dual catalytic performance of arene‐ruthenium amine complexes for norbornene ring‐opening metathesis and methyl methacrylate atom‐transfer radical polymerizations</atitle><jtitle>Applied organometallic chemistry</jtitle><date>2020-05</date><risdate>2020</risdate><volume>34</volume><issue>5</issue><epage>n/a</epage><issn>0268-2605</issn><eissn>1099-0739</eissn><abstract>Arene ruthenium(II) complexes bearing the cyclic amines RuCl2(η6‐p‐cymene)(pyrrolidine)] (1), [RuCl2(η6‐p‐cymene)(piperidine)] (2), and [RuCl2(η6‐p‐cymene)(peridroazepine)] (3) were successfully synthesized. Complexes 1–3 were fully characterized by means of Fourier transform infrared, UV–visible, and NMR spectroscopy, elemental analysis, cyclic voltammetry, computational methods, and one of the complexes was further studied by single crystal X‐ray crystallography. These compounds were evaluated as catalytic precursors for ring‐opening metathesis polymerization (ROMP) of norbornene (NBE) and atom‐transfer radical polymerization (ATRP) of methyl methacrylate (MMA). NBE polymerization via ROMP was evaluated using complexes 1–3 as precatalysts in the presence of ethyl diazoacetate (EDA) under different [NBE]/[EDA]/[Ru] ratios, temperatures (25 and 50°C), and reaction times (5–60 min). The highest yields of polyNBE were obtained with [NBE]/[EDA]/[Ru] = 5000/28/1 for 60 min at 50°C. MMA polymerization via ATRP was conducted using 1–3 as catalysts in the presence of ethyl‐α‐bromoisobutyrate (EBiB) as initiator. The catalytic tests were evaluated as a function of the reaction time using the initial molar ratio of [MMA]/[EBiB]/[Ru] = 1000/2/1 at 95°C. The increase in molecular weight as function of time indicates that complexes 1–3 were able to mediate the MMA polymerization with an acceptable rate and some level of control. Differences in the rate of polymerization were observed in the order 3 > 2 > 1 for the ROMP and ATRP.
A series of [RuCl2(p‐cymene)(amine)] complexes, where amine is pyrrolidine (1), piperidine (2), or perhydroazepine (3), were synthesized. The ruthenium complexes (1–3) were fully characterized by elemental analysis, FT‐IR, UV–Vis, NMR, XRD, cyclic voltammetry and computational studies. Complexes 1–3 have been successfully employed as catalytic precursors for ROMP of norbornene and ATRP of methyl methacrylate.</abstract><cop>Chichester</cop><pub>Wiley Subscription Services, Inc</pub><doi>10.1002/aoc.5602</doi><tpages>12</tpages><orcidid>https://orcid.org/0000-0001-8843-2841</orcidid><orcidid>https://orcid.org/0000-0003-4699-9481</orcidid></addata></record> |
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| subjects | Amines ATRP Chemical analysis Chemistry Crystallography Decomposition reactions Fourier transforms Infrared analysis Metathesis NMR spectroscopy olefin Piperidine Polymerization Polymethyl methacrylate p‐cymene Reaction time ROMP Ruthenium Ruthenium compounds Single crystals |
| title | Dual catalytic performance of arene‐ruthenium amine complexes for norbornene ring‐opening metathesis and methyl methacrylate atom‐transfer radical polymerizations |
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