Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes

Sai Puneet Desai, Jingyun Ye, Jian Zheng, Magali S. Ferrandon, Thomas E. Webber, Ana E. Platero-Prats, Jiaxin Duan, Paula Garcia-Holley, Donald M. Camaioni, Karena W. Chapman, Massimiliano Delferro, Omar K. Farha, John L. Fulton, Laura Gagliardi, Johannes A. Lercher, Lee Penn, Andreas Stein, Connie C. Lu

Research output: Contribution to journalArticle

11 Citations (Scopus)

Abstract

Promoters are ubiquitous in industrial heterogeneous catalysts. The wider roles of promoters in accelerating catalysis and/or controlling selectivity are, however, not well understood. A model system has been developed where a heterobimetallic active site comprising an active metal (Rh) and a promoter ion (Ga) is preassembled and delivered onto a metal-organic framework (MOF) support, NU-1000. The Rh-Ga sites in NU-1000 selectively catalyze the hydrogenation of acyclic alkynes to E-alkenes. The overall stereoselectivity is complementary to the well-known Lindlar's catalyst, which generates Z-alkenes. The role of the Ga in promoting this unusual selectivity is evidenced by the lack of semihydrogenation selectivity when Ga is absent and only Rh is present in the active site.

Original languageEnglish (US)
Pages (from-to)15309-15318
Number of pages10
JournalJournal of the American Chemical Society
Volume140
Issue number45
DOIs
StatePublished - Nov 14 2018

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Rhodium
Gallium
Alkynes
Alkenes
Olefins
Catalytic Domain
Metals
Stereoselectivity
Catalysts
Hydrogenation
Catalyst selectivity
Catalysis
Ions

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  • Shared

Reporting period for MRSEC

  • Period 5

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Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework : Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes. / Desai, Sai Puneet; Ye, Jingyun; Zheng, Jian; Ferrandon, Magali S.; Webber, Thomas E.; Platero-Prats, Ana E.; Duan, Jiaxin; Garcia-Holley, Paula; Camaioni, Donald M.; Chapman, Karena W.; Delferro, Massimiliano; Farha, Omar K.; Fulton, John L.; Gagliardi, Laura; Lercher, Johannes A.; Penn, Lee; Stein, Andreas; Lu, Connie C.

In: Journal of the American Chemical Society, Vol. 140, No. 45, 14.11.2018, p. 15309-15318.

Research output: Contribution to journalArticle

Desai, SP, Ye, J, Zheng, J, Ferrandon, MS, Webber, TE, Platero-Prats, AE, Duan, J, Garcia-Holley, P, Camaioni, DM, Chapman, KW, Delferro, M, Farha, OK, Fulton, JL, Gagliardi, L, Lercher, JA, Penn, L, Stein, A & Lu, CC 2018, 'Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes', Journal of the American Chemical Society, vol. 140, no. 45, pp. 15309-15318. https://doi.org/10.1021/jacs.8b08550
Desai, Sai Puneet ; Ye, Jingyun ; Zheng, Jian ; Ferrandon, Magali S. ; Webber, Thomas E. ; Platero-Prats, Ana E. ; Duan, Jiaxin ; Garcia-Holley, Paula ; Camaioni, Donald M. ; Chapman, Karena W. ; Delferro, Massimiliano ; Farha, Omar K. ; Fulton, John L. ; Gagliardi, Laura ; Lercher, Johannes A. ; Penn, Lee ; Stein, Andreas ; Lu, Connie C. / Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework : Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes. In: Journal of the American Chemical Society. 2018 ; Vol. 140, No. 45. pp. 15309-15318.
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AU - Stein, Andreas

AU - Lu, Connie C.

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