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(Referência obtida automaticamente do Web of Science, por meio da informação sobre o financiamento pela FAPESP e o número do processo correspondente, incluída na publicação pelos autores.)

Silanol-Assisted Carbinolamine Formation in an Amine-Functionalized Mesoporous Silica Surface: Theoretical Investigation by Fragmentation Methods

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Autor(es):
de Lima Batista, Ana P. [1] ; Zahariev, Federico [2, 3] ; Slowing, Igor I. [2, 3] ; Braga, Ataualpa A. C. [1] ; Ornellas, Fernando R. [1] ; Gordon, Mark S. [2, 3]
Número total de Autores: 6
Afiliação do(s) autor(es):
[1] Inst Quim, Dept Quim Fundamental, BR-05508000 Sao Paulo, SP - Brazil
[2] Iowa State Univ, Ames Lab, Ames, IA 50011 - USA
[3] Iowa State Univ, Dept Chem, Ames, IA 50011 - USA
Número total de Afiliações: 3
Tipo de documento: Artigo Científico
Fonte: Journal of Physical Chemistry B; v. 120, n. 8, p. 1660-1669, MAR 3 2016.
Citações Web of Science: 6
Resumo

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. (AU)

Processo FAPESP: 13/22235-0 - Catálise homogênea e heterogênea: a importância de grupos auxiliares
Beneficiário:Ana Paula de Lima Batista
Linha de fomento: Bolsas no Brasil - Pós-Doutorado