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1,2-H- versus 1,2-C-Shift on Sn-Silsesquioxanes

Josephson, Tyler R. and Brand, Stephen K. and Caratzoulas, Stavros and Vlachos, Dionisios G. (2017) 1,2-H- versus 1,2-C-Shift on Sn-Silsesquioxanes. ACS Catalysis, 7 (1). pp. 25-33. ISSN 2155-5435. doi:10.1021/acscatal.6b03128.

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Lewis acidic zeolites such as Sn-Beta catalyze glucose isomerization to fructose via an intramolecular 1,2-H-shift reaction, a key step for converting lignocellulosic biomass into renewable chemicals. Na-exchange of Sn-Beta titrates the neighboring SiOH group in the open Sn site and shifts catalyst selectivity to mannose formed by a 1,2-C-shift reaction. To probe structure/activity relationships in the zeolite, tin-containing silsesquioxanes with (1a) and without (1b) a neighboring SiOH group were recently synthesized and tested. These molecular catalysts are active for glucose conversion, and the presence (absence) of the SiOH favors fructose (mannose) selectivity by intramolecular H(C)-shift reactions. Using density functional theory, we investigated numerous H/C-shift pathways on these tin-silsesquioxane catalysts. On both 1a and 1b, the H-shift reaction occurs through a bidentate binding mode without participation of the SiOH, while the bidentate binding mode is not favored for the C-shift due to steric hindrance. Instead, the C-shift reaction occurs through different concerted reaction pathways, in which an acetylacetonate (acac) ligand interacts with the substrate in the transition state complexes. Favorable H-shift pathways without SiOH participation and acac ligand promotion of the C-shift pathway explain why 1a produces mannose from C-shift reactions instead of exclusively catalyzing H-shift reactions, as the Sn-Beta open site does.

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Additional Information:© 2016 American Chemical Society. Received: November 2, 2016; Published: November 15, 2016. Research was supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), under Award No. DE-SC0001004. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. T.R.J. wishes to acknowledge funding from the National Science Foundation Graduate Research Fellowship Program under Grant No. 0750966, as well as the George W. Laird Merit Fellowship. S.K.B. wishes to acknowledge funding from the National Science Foundation Graduate Research Fellowship Program under Grant No. DGE-1144469. Any opinions, findings, and conclusions or recommendations expressed in this material are those of the author(s) and do not necessarily reflect the views of the National Science Foundation. The authors thank Professor Mark Davis and Dr. Jeff Christianson for numerous useful conversations. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0001004
Department of Energy (DOE)DE-AC02-05CH11231
NSF Graduate Research FellowshipDGE-0750966
George W. Laird Merit FellowshipUNSPECIFIED
NSF Graduate Research FellowshipDGE-1144469
Subject Keywords:Bader; Bilik reaction; hydride transfer; Lewis acids; silsesquioxanes; zeolites
Issue or Number:1
Record Number:CaltechAUTHORS:20161128-160505736
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Official Citation:1,2-H- versus 1,2-C-Shift on Sn-Silsesquioxanes Tyler R. Josephson, Stephen K. Brand, Stavros Caratzoulas, and Dionisios G. Vlachos ACS Catalysis 2017 7 (1), 25-33 DOI: 10.1021/acscatal.6b03128
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:72347
Deposited By: Tony Diaz
Deposited On:29 Nov 2016 00:33
Last Modified:11 Nov 2021 05:00

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