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Hydrogenation of N-Heteroarenes Using Rhodium Precatalysts: Reductive Elimination Leads to Formation of Multimetallic Clusters

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.9b09540· OSTI ID:1569484
 [1];  [2];  [2];  [3];  [2]
  1. Princeton Univ., NJ (United States); Princeton University
  2. Princeton Univ., NJ (United States)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations
A rhodium-catalyzed method for the hydrogenation of N-heteroarenes is described here. A diverse array of unsubstituted N-heteroarenes including pyridine, pyrrole and pyrazine, traditionally challenging substrates for hydrogenation, were successfully hydrogenated using the organometallic precatalysts, (η5-C5Me5)Rh(N-C)H (N-C = 2-phenylpyridinyl (ppy) or benzo[h]quinolinyl (bq)). In addition, the hydrogenation of polyaromatic N-heteroarenes exhibited uncommon chemoselectivity. Studies into catalyst activation revealed that photochemical or thermal activation of (η5-C5Me5)Rh(bq)H induced C(sp2)–H reductive elimination and generated the bimetallic complex, [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H]. In the presence of H2 both of the (η5-C5Me5)Rh(N-C)H precursors and [(η5-C5Me5)Rh(µ2,η2-bq)Rh(η5-C5Me5)H] converted to a pentametallic rhodium hydride cluster, (η5-C5Me5)4Rh5H7, the structure of which was established by NMR spectroscopy, X-ray and neutron diffraction. Kinetic studies on pyridine hydrogenation were conducted with each of the isolated rhodium complexes to identify catalytically relevant species. The data are most consistent with hydrogenation catalysis prompted by an unobserved multimetallic cluster with formation of (η5-C5Me5)4Rh5H7 serving as a deactivation pathway.
Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Princeton Univ., NJ (United States)
Sponsoring Organization:
Deutsche Forschungsgemeinschaft (DFG); National Science Foundation (NSF); Natural Sciences and Engineering Research Council of Canada (NSERC); Samsung; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC05-00OR22725; SC0006498
OSTI ID:
1569484
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 44 Vol. 141; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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How to Conceptualize Catalytic Cycles? The Energetic Span Model journal February 2011
Controlled partial transfer hydrogenation of quinolines by cobalt-amido cooperative catalysis journal March 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY