Enhanced Activity from Coordinatively Unsaturated and Dynamic Zeolite-Bound Organoscandium Species

Southern, Scott A.; Li, Yuting; Liu, Da-Jiang; Sadow, Aaron D.; Qi, Long; Perras, Frédéric A.

doi:10.1021/acscatal.4c00678

Enhanced Activity from Coordinatively Unsaturated and Dynamic Zeolite-Bound Organoscandium Species

Journal Article · Fri Jun 07 00:00:00 EDT 2024 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.4c00678· OSTI ID:2371697

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Ames Laboratory (AMES), Ames, IA (United States)
Ames Laboratory (AMES), Ames, IA (United States); Iowa State University, Ames, IA (United States)

Scandium borohydride grafted into the micropores of the faujasite zeolite HY30 catalyzes the C–H borylation of benzene, whereas silica-grafted species are inactive. This catalytic activity may originate from grafting at a Brønsted acid site leading to a more electron-deficient rare earth center. Herein, we apply multinuclear double-resonance nuclear magnetic resonance (NMR) experiments to probe the structure and dynamics of zeolite- and silica-bound scandium borohydride complexes. The experiments reveal that scandium centers located within the zeolite micropores, in proximity to Al-created Brønsted sites, are more dynamic than rigid scandium sites grafted on silanols. Through a combination of NMR and molecular dynamics simulations, we show that the coordination of the scandium in the zeolite is labile, with the metal exchanging between two binding sites. As a result, the weak electron donation from the support that enables the movement of the Sc center leads to the formation of an undercoordinated metal center that cannot exist on silica, ultimately leading to the new catalytic activity of the species.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 2371697

Report Number(s):: IS-J--11,353

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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