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

doi:10.1021/jacs.8b08550

This content will become publicly available on October 23, 2019

Title: Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]

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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) are 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 Zalkenes. In conclusion, 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.

Authors:

Desai, Sai Puneet ^[1];

^[1];

^[2]; Ferrandon, Magali S. ^[3];

^[1];

^[4]; Duan, Jiaxin ^[1]; Garcia-Holley, Paula ^[5];

^[2];

^[6];

^[3];

^[5];

^[2];

^[1]; Lercher, Johannes A. ^[7];

^[1];

^[1]

Univ. of Minnesota, Minneapolis, MN (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. Autonoma de Madrid, Madrid (Spain); Argonne National Lab. (ANL), Argonne, IL (United States)
Northwestern Univ., Evanston, IL (United States)
Argonne National Lab. (ANL), Argonne, IL (United States); Stony Brook Univ., Stony Brook, NY (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); Technische Univ. Munchen, Garching (Germany)

Publication Date:: 2018-10-23

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

OSTI Identifier:: 1484223

Alternate Identifier(s):: OSTI ID: 1507435

Report Number(s):: PNNL-SA-137231
Journal ID: ISSN 0002-7863; 148161

Grant/Contract Number:: AC02-06CH11357; AC05-76RL01830

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 140; Journal Issue: 45; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    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, R. Lee, Stein, Andreas, and Lu, Connie C. Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes].  United States: N. p., 2018. 
        Web.  doi:10.1021/jacs.8b08550.

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                    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, R. 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 [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes].  United States.  doi:10.1021/jacs.8b08550.

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                    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, R. Lee, Stein, Andreas, and Lu, Connie C. Tue .  
        "Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]".  United States.  doi:10.1021/jacs.8b08550.

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@article{osti_1484223,

  title        = {Well-Defined Rhodium–Gallium Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes [Well-Defined Rh–Ga Catalytic Sites in a Metal–Organic Framework: Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes]},

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

  abstractNote = {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) are 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 Zalkenes. In conclusion, 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.},

  doi          = {10.1021/jacs.8b08550},

  journal      = {Journal of the American Chemical Society},

  number       = 45,

  volume       = 140,

  place        = {United States},

  year         = {2018},

  month        = {10}

}

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