TY - JOUR
T1 - Well-Defined Rhodium-Gallium Catalytic Sites in a Metal-Organic Framework
T2 - Promoter-Controlled Selectivity in Alkyne Semihydrogenation to E-Alkenes
AU - Desai, Sai Puneet
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, R. Lee
AU - Stein, Andreas
AU - Lu, Connie C.
N1 - Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/11/14
Y1 - 2018/11/14
N2 - 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.
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.
UR - http://www.scopus.com/inward/record.url?scp=85056503061&partnerID=8YFLogxK
U2 - 10.1021/jacs.8b08550
DO - 10.1021/jacs.8b08550
M3 - Article
C2 - 30352506
AN - SCOPUS:85056503061
SN - 0002-7863
VL - 140
SP - 15309
EP - 15318
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 45
ER -