Silanol-Assisted Carbinolamine Formation in an Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation by Fragmentation Methods de Lima Batista, Ana Zahariev, Federico Slowing, Igor Braga, Ataualpa Gordon, Mark Ornellas, Fernando
dc.contributor.department Ames National Laboratory
dc.contributor.department Chemistry 2018-02-17T13:44:11.000 2020-06-30T01:23:58Z 2020-06-30T01:23:58Z Thu Jan 01 00:00:00 UTC 2015 2015-12-15
dc.description.abstract <p>The aldol reaction catalyzed by an amine-substituted mesoporous silica nanoparticle (amine-MSN) surface was investigated using a large molecular cluster model (Si392O958C6NH361) combined with the surface integrated molecular orbital/molecular mechanics (SIMOMM) and fragment molecular orbital (FMO) methods. Three distinct pathways for the carbinolamine formation, the first step of the amine-catalyzed aldol reaction, are proposed and investigated in order to elucidate the role of the silanol environment on the catalytic capability of the amine-MSN material. The computational study reveals that the most likely mechanism involves the silanol groups actively participating in the reaction, forming and breaking covalent bonds in the carbinolamine step. Therefore, the active participation of MSN silanol groups in the reaction mechanism leads to a significant reduction in the overall energy barrier for the carbinolamine formation. In addition, a comparison between the findings using a minimal cluster model and the Si392O958C6NH361 cluster suggests that the use of larger models is important when heterogeneous catalysis problems are the target.</p>
dc.description.comments <p>Reprinted (adapted) with permission from <em>The Journal of Physical Chemistry B</em>, doi: <a href="" target="_blank">10.1021/acs.jpcb.5b08446</a>. Copyright 2015 American Chemical Society.</p>
dc.format.mimetype application/pdf
dc.identifier archive/
dc.identifier.articleid 1934
dc.identifier.contextkey 8190789
dc.identifier.s3bucket isulib-bepress-aws-west
dc.identifier.submissionpath chem_pubs/933
dc.language.iso en
dc.source.bitstream archive/|||Sat Jan 15 02:31:40 UTC 2022
dc.source.bitstream archive/|||Sat Jan 15 02:31:41 UTC 2022
dc.source.uri 10.1021/acs.jpcb.5b08446
dc.subject.disciplines Chemistry
dc.subject.disciplines Inorganic Chemistry
dc.subject.disciplines Organic Chemistry
dc.subject.disciplines Other Chemistry
dc.subject.disciplines Polymer Chemistry
dc.title Silanol-Assisted Carbinolamine Formation in an Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation by Fragmentation Methods
dc.type article
dc.type.genre article
dspace.entity.type Publication
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relation.isAuthorOfPublication 1a5927c0-5a5f-440e-86e0-9da8dc6afda0
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relation.isOrgUnitOfPublication 42864f6e-7a3d-4be3-8b5a-0ae3c3830a11
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