Single-Site Cobalt Catalysts at New Zr ₈ (μ ₂ -O) ₈ (μ ₂ -OH) ₄ Metal-Organic Framework Nodes for Highly Active Hydrogenation of Alkenes, Imines, Carbonyls, and Heterocycles

Journal Article · Wed Sep 21 00:00:00 EDT 2016 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b06759· OSTI ID:1337195

Ji, Pengfei; Manna, Kuntal; Lin, Zekai; Urban, Ania; Greene, Francis X.; Lan, Guangxu; Lin, Wenbin

We report here the synthesis of robust and porous metal–organic frameworks (MOFs), M-MTBC (M = Zr or Hf), constructed from the tetrahedral linker methane-tetrakis(p-biphenylcarboxylate) (MTBC) and two types of secondary building units (SBUs): cubic M₈(μ₂-O)₈(μ₂-OH)₄ and octahedral M6(μ₃-O)₄(μ₃-OH)₄. While the M₆-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M₈-SBU is composed of eight MIV ions in a cubic fashion linked by eight μ₂-oxo and four μ₂-OH groups. The metalation of Zr-MTBC SBUs with CoCl₂, followed by treatment with NaBEt₃H, afforded highly active and reusable solid Zr-MTBC-CoH catalysts for the hydrogenation of alkenes, imines, carbonyls, and heterocycles. Zr-MTBC-CoH was impressively tolerant of a range of functional groups and displayed high activity in the hydrogenation of tri- and tetra-substituted alkenes with TON > 8000 for the hydrogenation of 2,3-dimethyl-2-butene. Our structural and spectroscopic studies show that site isolation of and open environments around the cobalt-hydride catalytic species at Zr₈-SBUs are responsible for high catalytic activity in the hydrogenation of a wide range of challenging substrates. MOFs thus provide a novel platform for discovering and studying new single-site base-metal solid catalysts with enormous potential for sustainable chemical synthesis.

• Research Organization: Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
• Sponsoring Organization: USDOE; National Science Foundation (NSF)
• OSTI ID: 1337195
• Journal Information: Journal of the American Chemical Society, Vol. 138, Issue 37; ISSN 0002-7863
• Publisher: American Chemical Society (ACS)
• Country of Publication: United States
• Language: ENGLISH

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY