Silanol-assisted carbinolamine formation in an amine-functionalized mesoporous silica surface: Theoretical investigation by fragmentation methods

de Lima Batista, Ana P.; Zahariev, Federico; Slowing, Igor I.; Braga, Ataualpa A. C.; Ornellas, Fernando R.; Gordon, Mark S.

doi:10.1021/acs.jpcb.5b08446

Title: Silanol-assisted carbinolamine formation in an amine-functionalized mesoporous silica surface: Theoretical investigation by fragmentation methods

Journal Article · Tue Dec 15 00:00:00 EST 2015 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.5b08446· OSTI ID:1234538

de Lima Batista, Ana P. ^[1]; Zahariev, Federico ^[2]; Slowing, Igor I. ^[2]; Braga, Ataualpa A. C. ^[1]; Ornellas, Fernando R. ^[1]; Gordon, Mark S. ^[2]

Instituto de Quimica, Sao Paulo (Brazil)
Iowa State Univ., Ames, IA (United States)

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. Here 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. Furthermore, 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.

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Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: 236761/2012-9; 2013/22235-0; AC02-07CH11358

OSTI ID:: 1234538

Report Number(s):: IS-J-8869

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Journal Name: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 17 works

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References (62)

A green look at the aldol reaction Mestres, Ramon Green Chemistry, Vol. 6, Issue 12 https://doi.org/10.1039/b409143b	journal	January 2004
Solid Acids as Heterogeneous Support for Primary Amino Acid-Derived Diamines in Direct Asymmetric Aldol Reactions Demuynck, Anneleen L. W.; Peng, Li; de Clippel, Filip Advanced Synthesis & Catalysis, Vol. 353, Issue 5 https://doi.org/10.1002/adsc.201000871	journal	March 2011
Tuning acid–base cooperativity to create next generation silica-supported organocatalysts Brunelli, Nicholas A.; Jones, Christopher W. Journal of Catalysis, Vol. 308 https://doi.org/10.1016/j.jcat.2013.05.022	journal	December 2013
Recyclable silica-supported prolinamide organocatalysts for direct asymmetric Aldol reaction in water Monge-Marcet, Amàlia; Cattoën, Xavier; Alonso, Diego A. Green Chemistry, Vol. 14, Issue 6 https://doi.org/10.1039/c2gc35227c	journal	January 2012
Cooperative Catalysis by General Acid and Base Bifunctionalized Mesoporous Silica Nanospheres Huh, Seong; Chen, Hung-Ting; Wiench, Jerzy W. Angewandte Chemie International Edition, Vol. 44, Issue 12 https://doi.org/10.1002/anie.200462424	journal	March 2005
Exploration of acid–base geometric influence on cooperative activation for aldol reaction Liu, Bo; Liu, Heng; Wang, Chunhua Applied Catalysis A: General, Vol. 443-444 https://doi.org/10.1016/j.apcata.2012.06.020	journal	November 2012
Optimizing the matching between the acid and the base of cooperative catalysis to inhibit dehydration in the aldol condensation Liu, Bo; Wu, Shujie; Yu, Xiaofang Journal of Colloid and Interface Science, Vol. 362, Issue 2 https://doi.org/10.1016/j.jcis.2011.06.068	journal	October 2011
Silica-Bound Homogenous Catalysts as Recoverable and Reusable Catalysts in Organic Synthesis Corma, Avelino; Garcia, Hermenegildo Advanced Synthesis & Catalysis, Vol. 348, Issue 12-13 https://doi.org/10.1002/adsc.200606192	journal	August 2006
A molecular view of heterogeneous catalysis Christensen, Claus Hviid; Nørskov, Jens K. The Journal of Chemical Physics, Vol. 128, Issue 18 https://doi.org/10.1063/1.2839299	journal	May 2008
Tailoring nanohybrids and nanocomposites for catalytic applications de Clippel, Filip; Dusselier, Michiel; Van de Vyver, Stijn Green Chemistry, Vol. 15, Issue 6 https://doi.org/10.1039/c3gc37141g	journal	January 2013
Cooperative catalysis by silica-supported organic functional groups Margelefsky, Eric L.; Zeidan, Ryan K.; Davis, Mark E. Chemical Society Reviews, Vol. 37, Issue 6 https://doi.org/10.1039/b710334b	journal	January 2008
Recent Advances in Catalysis Over Mesoporous Molecular Sieves Martín-Aranda, Rosa M.; Čejka, Jiří Topics in Catalysis, Vol. 53, Issue 3-4 https://doi.org/10.1007/s11244-009-9419-6	journal	December 2009
Knoevenagel and aldol condensations catalysed by a new diamino-functionalised mesoporous material Choudary, B. M.; Kantam, M. Lakshmi; Sreekanth, P. Journal of Molecular Catalysis A: Chemical, Vol. 142, Issue 3 https://doi.org/10.1016/S1381-1169(98)00301-X	journal	June 1999
Fine Chemical Synthesis Through Supported Bases Maggi, R.; Sartori, G.; Oro, C. Current Organic Chemistry, Vol. 12, Issue 7 https://doi.org/10.2174/138527208784245969	journal	May 2008
Enhanced Effect of Mesoporous Silica on Base-Catalyzed Aldol Reaction Kubota, Yoshihiro; Goto, Kunio; Miyata, Shintaro Chemistry Letters, Vol. 32, Issue 3 https://doi.org/10.1246/cl.2003.234	journal	March 2003
Efficient solid-base catalysts for aldol reaction by optimizing the density and type of organoamine groups on nanoporous silica Xie, Youwei; Sharma, Krishna K.; Anan, Abhishek Journal of Catalysis, Vol. 265, Issue 2 https://doi.org/10.1016/j.jcat.2009.04.018	journal	July 2009
Further Investigations on the Promoting Effect of Mesoporous Silica on Base-Catalyzed Aldol Reaction Kubota, Y.; Yamaguchi, H.; Yamada, T. Topics in Catalysis, Vol. 53, Issue 7-10 https://doi.org/10.1007/s11244-010-9477-9	journal	April 2010
The effect of acid–base pairing on catalysis: An efficient acid–base functionalized catalyst for aldol condensation Zeidan, R.; Davis, M. Journal of Catalysis, Vol. 247, Issue 2 https://doi.org/10.1016/j.jcat.2007.02.005	journal	April 2007
Substrate inhibition in the heterogeneous catalyzed aldol condensation: A mechanistic study of supported organocatalysts Kandel, Kapil; Althaus, Stacey M.; Peeraphatdit, Chorthip Journal of Catalysis, Vol. 291 https://doi.org/10.1016/j.jcat.2012.04.005	journal	July 2012
Solvent-Induced Reversal of Activities between Two Closely Related Heterogeneous Catalysts in the Aldol Reaction Kandel, Kapil; Althaus, Stacey M.; Peeraphatdit, Chorthip ACS Catalysis, Vol. 3, Issue 2 https://doi.org/10.1021/cs300748g	journal	January 2013
Using a Reactive Force Field To Correlate Mobilities Obtained from Solid-State ¹³ C NMR on Mesoporous Silica Nanoparticle Systems Nedd, Sean; Kobayashi, Takeshi; Tsai, Chih-Hsiang The Journal of Physical Chemistry C, Vol. 115, Issue 33 https://doi.org/10.1021/jp204510m	journal	August 2011
SIMOMM: An Integrated Molecular Orbital/Molecular Mechanics Optimization Scheme for Surfaces Shoemaker, James R.; Gordon, Mark S. The Journal of Physical Chemistry A, Vol. 103, Issue 17 https://doi.org/10.1021/jp982600e	journal	April 1999
Comparative Study of Surface Cycloadditions of Ethylene and 2-Butene on the Si(100)-2 × 1 Surface Lee, Hee Soon; Choi, Cheol Ho; Gordon, Mark S. The Journal of Physical Chemistry B, Vol. 109, Issue 11 https://doi.org/10.1021/jp0501345	journal	March 2005
Cycloaddition Isomerizations of Adsorbed 1,3-Cyclohexadiene on Si(100)-2×1 Surface: First Neighbor Interactions Lee, Hee Soon; Choi, Cheol Ho; Gordon, Mark S. Journal of the American Chemical Society, Vol. 127, Issue 23 https://doi.org/10.1021/ja050568d	journal	June 2005
Surface Reaction of 1,2,-Dichloroethylene on Si(100)-2 × 1: Importance of Surface Isomerization Channel Ghosh, Manik Kumer; Sarker, Majher Ibna Mannan; Choi, Cheol Ho The Journal of Physical Chemistry C, Vol. 112, Issue 25 https://doi.org/10.1021/jp076526o	journal	May 2008
Theoretical Study of Initial Adsorptions and Subsequent Surface Rearrangements of H−C≡C−OH on Si(100)-2 × 1 Surface Ghosh, Manik Kumer; Choi, Cheol Ho The Journal of Physical Chemistry C, Vol. 114, Issue 33 https://doi.org/10.1021/jp104186w	journal	July 2010
The concerted and stepwise chemisorption mechanisms of isothiazole and thiazole on Si(100)−2 × 1 surface Ghosh, Manik Kumer; Choi, Cheol Ho Theoretical Chemistry Accounts, Vol. 130, Issue 2-3 https://doi.org/10.1007/s00214-011-1035-4	journal	September 2011
Adsorption mechanisms of isoxazole and oxazole on Si(100)-2 × 1 surface: Si–N dative bond addition vs. [4+2] cycloaddition Kumer Ghosh, Manik; Choi, Cheol Ho The Journal of Chemical Physics, Vol. 135, Issue 24 https://doi.org/10.1063/1.3671454	journal	December 2011
Fragment molecular orbital method: an approximate computational method for large molecules Kitaura, Kazuo; Ikeo, Eiji; Asada, Toshio Chemical Physics Letters, Vol. 313, Issue 3-4 https://doi.org/10.1016/S0009-2614(99)00874-X	journal	November 1999
Efficient and Accurate Fragmentation Methods Pruitt, Spencer R.; Bertoni, Colleen; Brorsen, Kurt R. Accounts of Chemical Research, Vol. 47, Issue 9 https://doi.org/10.1021/ar500097m	journal	May 2014
Covalent Bond Fragmentation Suitable To Describe Solids in the Fragment Molecular Orbital Method Fedorov, Dmitri G.; Jensen, Jan H.; Deka, Ramesh C. The Journal of Physical Chemistry A, Vol. 112, Issue 46 https://doi.org/10.1021/jp805435n	journal	November 2008
Analytic gradient for the adaptive frozen orbital bond detachment in the fragment molecular orbital method Fedorov, Dmitri G.; Avramov, Pavel V.; Jensen, Jan H. Chemical Physics Letters, Vol. 477, Issue 1-3 https://doi.org/10.1016/j.cplett.2009.06.072	journal	July 2009
Diffusion energy profiles in silica mesoporous molecular sieves modelled with the fragment molecular orbital method Roskop, Luke; Fedorov, Dmitri G.; Gordon, Mark S. Molecular Physics, Vol. 111, Issue 9-11 https://doi.org/10.1080/00268976.2013.780102	journal	March 2013
Modeling of peptide–silica interaction based on four-body corrected fragment molecular orbital (FMO4) calculations Okiyama, Yoshio; Tsukamoto, Takayuki; Watanabe, Chiduru Chemical Physics Letters, Vol. 566 https://doi.org/10.1016/j.cplett.2013.02.020	journal	April 2013
Conformations of Silica-Bound (Pentafluorophenyl)propyl Groups Determined by Solid-State NMR Spectroscopy and Theoretical Calculations Mao, Kanmi; Kobayashi, Takeshi; Wiench, Jerzy W. Journal of the American Chemical Society, Vol. 132, Issue 35 https://doi.org/10.1021/ja105007b	journal	September 2010
Synergic catalytic effects in confined spaces Yu, Chenguang; He, Jing Chemical Communications, Vol. 48, Issue 41 https://doi.org/10.1039/c2cc31585h	journal	January 2012
How does confinement affect the catalytic activity of mesoporous materials? Goettmann, Frédéric; Sanchez, Clément J. Mater. Chem., Vol. 17, Issue 1 https://doi.org/10.1039/B608748P	journal	January 2007
Inhomogeneous Electron Gas Hohenberg, P.; Kohn, W. Physical Review, Vol. 136, Issue 3B, p. B864-B871 https://doi.org/10.1103/PhysRev.136.B864	journal	November 1964
Self-Consistent Equations Including Exchange and Correlation Effects Kohn, W.; Sham, L. J. Physical Review, Vol. 140, Issue 4A, p. A1133-A1138 https://doi.org/10.1103/PhysRev.140.A1133	journal	November 1965
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals Zhao, Yan; Truhlar, Donald G. Theoretical Chemistry Accounts, Vol. 120, Issue 1-3 https://doi.org/10.1007/s00214-007-0310-x	journal	July 2007
Self—Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian—Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules Hehre, W. J.; Ditchfield, R.; Pople, J. A. The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261 https://doi.org/10.1063/1.1677527	journal	March 1972
Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements Francl, Michelle M.; Pietro, William J.; Hehre, Warren J. The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665 https://doi.org/10.1063/1.444267	journal	October 1982
Algorithms and accuracy requirements for computing reaction paths by the method of steepest descent Garrett, Bruce C.; Redmon, Michael J.; Steckler, Rozeanne The Journal of Physical Chemistry, Vol. 92, Issue 6 https://doi.org/10.1021/j100317a022	journal	March 1988
An improved algorithm for reaction path following Gonzalez, Carlos; Schlegel, H. Bernhard The Journal of Chemical Physics, Vol. 90, Issue 4 https://doi.org/10.1063/1.456010	journal	February 1989
Molecular mechanics. The MM3 force field for hydrocarbons. 1 Allinger, Norman L.; Yuh, Young H.; Lii, Jenn Huei Journal of the American Chemical Society, Vol. 111, Issue 23 https://doi.org/10.1021/ja00205a001	journal	November 1989
Molecular mechanics. The MM3 force field for hydrocarbons. 2. Vibrational frequencies and thermodynamics Lii, Jenn Huei; Allinger, Norman L. Journal of the American Chemical Society, Vol. 111, Issue 23 https://doi.org/10.1021/ja00205a002	journal	November 1989
Molecular mechanics. The MM3 force field for hydrocarbons. 3. The van der Waals' potentials and crystal data for aliphatic and aromatic hydrocarbons Lii, Jenn Huei; Allinger, Norman L. Journal of the American Chemical Society, Vol. 111, Issue 23 https://doi.org/10.1021/ja00205a003	journal	November 1989
An efficient newton-like method for molecular mechanics energy minimization of large molecules Ponder, Jay W.; Richards, Frederic M. Journal of Computational Chemistry, Vol. 8, Issue 7 https://doi.org/10.1002/jcc.540080710	journal	October 1987
General atomic and molecular electronic structure system Schmidt, Michael W.; Baldridge, Kim K.; Boatz, Jerry A. Journal of Computational Chemistry, Vol. 14, Issue 11, p. 1347-1363 https://doi.org/10.1002/jcc.540141112	journal	November 1993
Fragment molecular orbital method: application to polypeptides Nakano, Tatsuya; Kaminuma, Tsuguchika; Sato, Toshiyuki Chemical Physics Letters, Vol. 318, Issue 6 https://doi.org/10.1016/S0009-2614(00)00070-1	journal	March 2000
Note on an Approximation Treatment for Many-Electron Systems Møller, Chr.; Plesset, M. S. Physical Review, Vol. 46, Issue 7 https://doi.org/10.1103/PhysRev.46.618	journal	October 1934
A parallel second-order Møller-Plesset gradient Fletcher, By GRAHAM D.; Rendell, Alistair P.; Sherwood, Paul Molecular Physics, Vol. 91, Issue 3 https://doi.org/10.1080/002689797171328	journal	June 1997
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Modeling Systems with π–π Interactions Using the Hartree–Fock Method with an Empirical Dispersion Correction Conrad, Justin A.; Gordon, Mark S. The Journal of Physical Chemistry A, Vol. 119, Issue 21 https://doi.org/10.1021/jp510288k	journal	December 2014
Macmolplt: a graphical user interface for GAMESS Bode, Brett M.; Gordon, Mark S. Journal of Molecular Graphics and Modelling, Vol. 16, Issue 3, p. 133-138 https://doi.org/10.1016/S1093-3263(99)00002-9	journal	June 1998
A fifth-order perturbation comparison of electron correlation theories Raghavachari, Krishnan; Trucks, Gary W.; Pople, John A. Chemical Physics Letters, Vol. 157, Issue 6 https://doi.org/10.1016/S0009-2614(89)87395-6	journal	May 1989
Efficient computer implementation of the renormalized coupled-cluster methods: The R-CCSD[T], R-CCSD(T), CR-CCSD[T], and CR-CCSD(T) approaches Piecuch, Piotr; Kucharski, Stanisław A.; Kowalski, Karol Computer Physics Communications, Vol. 149, Issue 2 https://doi.org/10.1016/S0010-4655(02)00598-2	journal	December 2002
Insights on Co-Catalyst-Promoted Enamine Formation between Dimethylamine and Propanal through Ab Initio and Density Functional Theory Study Patil, Mahendra P.; Sunoj, Raghavan B. The Journal of Organic Chemistry, Vol. 72, Issue 22 https://doi.org/10.1021/jo071004q	journal	October 2007
Binding and Diffusion of Al Adatoms and Dimers on the Si(100)-2 × 1 Reconstructed Surface: A Hybrid QM/MM Embedded Cluster Study Zorn, Deborah D.; Albao, Marvin A.; Evans, J. W. The Journal of Physical Chemistry C, Vol. 113, Issue 17 https://doi.org/10.1021/jp8105937	journal	April 2009
A Correlation of Reaction Rates Hammond, George S. Journal of the American Chemical Society, Vol. 77, Issue 2 https://doi.org/10.1021/ja01607a027	journal	January 1955
Fragmentation Methods: A Route to Accurate Calculations on Large Systems Gordon, Mark S.; Fedorov, Dmitri G.; Pruitt, Spencer R. Chemical Reviews, Vol. 112, Issue 1 https://doi.org/10.1021/cr200093j	journal	August 2011
Electron-correlated fragment-molecular-orbital calculations for biomolecular and nano systems Tanaka, Shigenori; Mochizuki, Yuji; Komeiji, Yuto Phys. Chem. Chem. Phys., Vol. 16, Issue 22 https://doi.org/10.1039/c4cp00316k	journal	January 2014

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