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Deciphering a Reaction Network for the Switchable Production of Tetrahydroquinoline or Quinoline with MOF-Supported Pd Tandem Catalysts

Journal Article · · ACS Catalysis
 [1];  [2];  [1];  [3];  [3];  [1];  [4];  [4];  [4];  [4];  [4];  [1]
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States)
  2. Zhejiang Univ., Hangzhou (China); Ames Lab., and Iowa State Univ., Ames, IA (United States)
  3. Iowa State Univ., Ames, IA (United States)
  4. Zhejiang Univ., Hangzhou (China)
+ Show Author Affiliations

A mechanistic study of heterogeneous tandem catalytic systems is crucial for understanding and improving catalyst activity and selectivity but remains challenging. Here, we demonstrate that a thorough mechanistic study of a multistep reaction can guide us to the controllable selective synthesis of phenyltetrahydroquinoline or phenylquinoline with easily accessible precursors. The one-pot production can be achieved, catalyzed by a well-defined, bifunctional metal–organic framework-supported Pd nanoparticles, with only water as the side product. Our mechanistic study identifies six transient intermediates and ten transformation steps from the operando magic angle spinning nuclear magnetic resonance study under 27.6 bar H2. In particular, reactive intermediate 2-phenyl-3,4-dihydroquinoline cannot be observed with conventional chromatographic techniques but is found to reach the maximal concentration of 0.11 mol L–1 under the operando condition. The most probable reaction network is further deduced based on the kinetic information of reaction species, obtained from both operando and ex situ reaction studies. This deep understanding of the complex reaction network enables the kinetic control of the conversions of key intermediate, 2-phenyl-3,4-dihydroquinoline, with the addition of a homogeneous co-catalyst, allowing the selective production of tetrahydroquinoline or quinoline on demand. Finally, the demonstrated methods in this work open up new avenues toward efficient modulation of reactions with a complex network to achieve desired selectivities.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences, & Biosciences Division; National Key Research and Development Program of China; National Natural Science Foundation of China (NNSFC); National Science Foundation (NSF)
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1616739
Report Number(s):
IS-J--10,207
Journal Information:
ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 10 Vol. 10; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
mechanistic study
metal nanoparticles
metal-organic frameworks
operando spectroscopy
reaction network
tandem catalysis