Role(s) of TMA in polymerization
Quenched-flow data for propene polymerization with rac -Me 2 Si(2-Me-4-Ph-1-indenyl) 2 ZrCl 2 /MAO support a picture where removal of MAO qualitatively changes the kinetic profile from a mainly enthalpic to a mainly entropic barrier. DFT studies suggest that a not previously recognized singly-bridge...
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| Veröffentlicht in: | Dalton transactions : an international journal of inorganic chemistry 2016-04, Vol.45 (16), p.6847-6855 |
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| container_title | Dalton transactions : an international journal of inorganic chemistry |
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| creator | Ehm, C Cipullo, R Budzelaar, P. H. M Busico, V |
| description | Quenched-flow data for propene polymerization with
rac
-Me
2
Si(2-Me-4-Ph-1-indenyl)
2
ZrCl
2
/MAO support a picture where removal of MAO qualitatively changes the kinetic profile from a mainly enthalpic to a mainly entropic barrier. DFT studies suggest that a not previously recognized singly-bridged end-on coordination mode of Me
6
Al
2
to catalytically active centers may be kinetically relevant as a resting state. In contrast, the more traditional doubly-bridged complex of Me
3
Al is proposed to be more relevant to chain transfer to cocatalyst.
A new TMA-metallocene binding mode is presented and its role in entropy compensation in insertion chemistry discussed. |
| doi_str_mv | 10.1039/c5dt04895h |
| format | Article |
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rac
-Me
2
Si(2-Me-4-Ph-1-indenyl)
2
ZrCl
2
/MAO support a picture where removal of MAO qualitatively changes the kinetic profile from a mainly enthalpic to a mainly entropic barrier. DFT studies suggest that a not previously recognized singly-bridged end-on coordination mode of Me
6
Al
2
to catalytically active centers may be kinetically relevant as a resting state. In contrast, the more traditional doubly-bridged complex of Me
3
Al is proposed to be more relevant to chain transfer to cocatalyst.
A new TMA-metallocene binding mode is presented and its role in entropy compensation in insertion chemistry discussed.</description><identifier>ISSN: 1477-9226</identifier><identifier>EISSN: 1477-9234</identifier><identifier>DOI: 10.1039/c5dt04895h</identifier><identifier>PMID: 26846331</identifier><language>eng</language><publisher>England</publisher><subject>Barriers ; Catalysis ; Chain transfer ; Pictures ; Polymerization ; Reaction kinetics</subject><ispartof>Dalton transactions : an international journal of inorganic chemistry, 2016-04, Vol.45 (16), p.6847-6855</ispartof><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><citedby>FETCH-LOGICAL-c408t-de158af5fd089383311c70eb4afc5c4c492e737ad73ab1c48c5acc4501ead5ec3</citedby><cites>FETCH-LOGICAL-c408t-de158af5fd089383311c70eb4afc5c4c492e737ad73ab1c48c5acc4501ead5ec3</cites></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/26846331$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Ehm, C</creatorcontrib><creatorcontrib>Cipullo, R</creatorcontrib><creatorcontrib>Budzelaar, P. H. M</creatorcontrib><creatorcontrib>Busico, V</creatorcontrib><title>Role(s) of TMA in polymerization</title><title>Dalton transactions : an international journal of inorganic chemistry</title><addtitle>Dalton Trans</addtitle><description>Quenched-flow data for propene polymerization with
rac
-Me
2
Si(2-Me-4-Ph-1-indenyl)
2
ZrCl
2
/MAO support a picture where removal of MAO qualitatively changes the kinetic profile from a mainly enthalpic to a mainly entropic barrier. DFT studies suggest that a not previously recognized singly-bridged end-on coordination mode of Me
6
Al
2
to catalytically active centers may be kinetically relevant as a resting state. In contrast, the more traditional doubly-bridged complex of Me
3
Al is proposed to be more relevant to chain transfer to cocatalyst.
A new TMA-metallocene binding mode is presented and its role in entropy compensation in insertion chemistry discussed.</description><subject>Barriers</subject><subject>Catalysis</subject><subject>Chain transfer</subject><subject>Pictures</subject><subject>Polymerization</subject><subject>Reaction kinetics</subject><issn>1477-9226</issn><issn>1477-9234</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2016</creationdate><recordtype>article</recordtype><recordid>eNqFkE1Lw0AQhhdRbK1evCs5ViG6sx_d3WOpHxUqgtRz2E42GEm6dTc51F9vams9yhxm4H14Bx5CzoHeAOXmFmXeUKGNfD8gfRBKpYZxcbi_2ahHTmL8oJQxKtkx6bGRFiPOoU-SV1-5YbxKfJHMn8dJuUxWvlrXLpRftin98pQcFbaK7my3B-Tt4X4-maazl8enyXiWoqC6SXMHUttCFjnVhuuuG1BRtxC2QIkChWFOcWVzxe0CUGiUFlFICs7m0iEfkOG2dxX8Z-tik9VlRFdVdul8GzPQtBsD0vyPqu4_1wAb9HqLYvAxBldkq1DWNqwzoNlGXjaRd_MfedMOvtz1tova5Xv011YHXGyBEHGf_tnn38OkcXY</recordid><startdate>20160428</startdate><enddate>20160428</enddate><creator>Ehm, C</creator><creator>Cipullo, R</creator><creator>Budzelaar, P. H. M</creator><creator>Busico, V</creator><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope><scope>7QF</scope><scope>7SR</scope><scope>7U5</scope><scope>8BQ</scope><scope>8FD</scope><scope>JG9</scope><scope>L7M</scope></search><sort><creationdate>20160428</creationdate><title>Role(s) of TMA in polymerization</title><author>Ehm, C ; Cipullo, R ; Budzelaar, P. H. M ; Busico, V</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c408t-de158af5fd089383311c70eb4afc5c4c492e737ad73ab1c48c5acc4501ead5ec3</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2016</creationdate><topic>Barriers</topic><topic>Catalysis</topic><topic>Chain transfer</topic><topic>Pictures</topic><topic>Polymerization</topic><topic>Reaction kinetics</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Ehm, C</creatorcontrib><creatorcontrib>Cipullo, R</creatorcontrib><creatorcontrib>Budzelaar, P. H. M</creatorcontrib><creatorcontrib>Busico, V</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>MEDLINE - Academic</collection><collection>Aluminium Industry Abstracts</collection><collection>Engineered Materials Abstracts</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>Dalton transactions : an international journal of inorganic chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Ehm, C</au><au>Cipullo, R</au><au>Budzelaar, P. H. M</au><au>Busico, V</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Role(s) of TMA in polymerization</atitle><jtitle>Dalton transactions : an international journal of inorganic chemistry</jtitle><addtitle>Dalton Trans</addtitle><date>2016-04-28</date><risdate>2016</risdate><volume>45</volume><issue>16</issue><spage>6847</spage><epage>6855</epage><pages>6847-6855</pages><issn>1477-9226</issn><eissn>1477-9234</eissn><abstract>Quenched-flow data for propene polymerization with
rac
-Me
2
Si(2-Me-4-Ph-1-indenyl)
2
ZrCl
2
/MAO support a picture where removal of MAO qualitatively changes the kinetic profile from a mainly enthalpic to a mainly entropic barrier. DFT studies suggest that a not previously recognized singly-bridged end-on coordination mode of Me
6
Al
2
to catalytically active centers may be kinetically relevant as a resting state. In contrast, the more traditional doubly-bridged complex of Me
3
Al is proposed to be more relevant to chain transfer to cocatalyst.
A new TMA-metallocene binding mode is presented and its role in entropy compensation in insertion chemistry discussed.</abstract><cop>England</cop><pmid>26846331</pmid><doi>10.1039/c5dt04895h</doi><tpages>9</tpages></addata></record> |
| fulltext | fulltext |
| identifier | ISSN: 1477-9226 |
| ispartof | Dalton transactions : an international journal of inorganic chemistry, 2016-04, Vol.45 (16), p.6847-6855 |
| issn | 1477-9226 1477-9234 |
| language | eng |
| recordid | cdi_proquest_miscellaneous_1808089159 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Barriers Catalysis Chain transfer Pictures Polymerization Reaction kinetics |
| title | Role(s) of TMA in polymerization |
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