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

doi:10.1021/jacs.8b08550

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

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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 language	English (US)
Pages (from-to)	15309-15318
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	140
Issue number	45
DOIs	https://doi.org/10.1021/jacs.8b08550
State	Published - Nov 14 2018

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© 2018 American Chemical Society.

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Desai, S. P., Ye, J., Zheng, J., Ferrandon, M. S., Webber, T. E., Platero-Prats, A. E., Duan, J., Garcia-Holley, P., Camaioni, D. M., Chapman, K. W., Delferro, M., Farha, O. K., Fulton, J. L., Gagliardi, L., Lercher, J. A., Penn, L., Stein, A., & Lu, C. C. (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, 140(45), 15309-15318. https://doi.org/10.1021/jacs.8b08550

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

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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.",

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

note = "Publisher Copyright: {\textcopyright} 2018 American Chemical Society.",

year = "2018",

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doi = "10.1021/jacs.8b08550",

language = "English (US)",

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AU - Ye, Jingyun

AU - Zheng, Jian

AU - Ferrandon, Magali S.

AU - Webber, Thomas E.

AU - Platero-Prats, Ana E.

AU - Duan, Jiaxin

AU - Garcia-Holley, Paula

AU - Camaioni, Donald M.

AU - Chapman, Karena W.

AU - Delferro, Massimiliano

AU - Farha, Omar K.

AU - Fulton, John L.

AU - Gagliardi, Laura

AU - Lercher, Johannes A.

AU - Penn, Lee

AU - Stein, Andreas

AU - Lu, Connie C.

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AB - 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.

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

Abstract

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