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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

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

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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]
Total Authors: 6
[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
Total Affiliations: 3
Document type: Journal article
Source: Journal of Physical Chemistry B; v. 120, n. 8, p. 1660-1669, MAR 3 2016.
Web of Science Citations: 6

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)

FAPESP's process: 13/22235-0 - Homogeneous and Heterogeneous Catalysis: The Importance of Auxiliary Groups
Grantee:Ana Paula de Lima Batista
Support Opportunities: Scholarships in Brazil - Post-Doctorate