Matches in SemOpenAlex for { <https://semopenalex.org/work/W2921568354> ?p ?o ?g. }
- W2921568354 endingPage "3337" @default.
- W2921568354 startingPage "3327" @default.
- W2921568354 abstract "The intrinsic heterogeneity of alumina (Al2O3) surface presents a challenge for the development of alumina-supported single-site heterogeneous catalysts and hinders the characterization of catalytic species at the molecular level as well as the elucidation of mechanistic details of the catalytic reactions. Here we report the use of aluminum hydroxide secondary building units (SBUs) in the MIL-53(Al) metal–organic framework (MOF) with the formula Al(μ2–OH)(BDC) (BDC = 1,4-benzenedicarboxylate) as a uniform and structurally defined functional mimic of Al2O3 surface for supporting Earth-abundant metal (EAM) catalysts. The μ2–OH groups in MIL-53(Al) SBUs were readily deprotonated and metalated with CoCl2 and FeCl2 to afford MIL-53(Al)-CoCl and MIL-53(Al)-FeCl precatalysts which were characterized by powder X-ray diffraction, nitrogen sorption, elemental analysis, density functional theory, and extended X-ray fine structure spectroscopy. Activation with NaBEt3H converted MIL-53(Al)-CoCl to MIL-53(Al)-CoH which effectively catalyzed hydroboration of alkynes and nitriles and hydrosilylation of esters. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of AlIII and CoII centers in MIL-53(Al)-CoH while deuterium labeling studies suggested σ-bond metathesis as a key step for the MIL-53(Al)-CoH-catalyzed addition reactions. MIL-53(Al)-FeCl competently catalyzed oxidative Csp3–H amination and Wacker-type alkene oxidation. XANES analysis revealed the oxidation of FeII to FeIII centers in the activated MIL-53(Al)-FeCl catalyst and suggested that oxidative Csp3–H amination occurs via the formation of FeIII–OtBu species by single electron transfer between FeII centers in MIL-53(Al)-FeCl and (tBuO)2 with concomitant generation of 1 equiv of tBuO· radical, C–H activation through hydrogen atom abstraction to generate alkyl radicals, protonation of FeIII–OtBu by aniline to generate MIL-53(Al)-FeIII-anilide, and finally C–N coupling between the FeIII-anilide and alkyl radical to form the Csp3–H amination product and regenerate the FeII catalyst. These highly active single-site MOF-based solid catalysts were readily recovered and reused up to five times without significant decrease in catalytic activity. This work thus demonstrates the great potential of using the aluminum hydroxide SBUs in MOFs to support EAM catalysts for important organic transformations." @default.
- W2921568354 created "2019-03-22" @default.
- W2921568354 creator A5003313770 @default.
- W2921568354 creator A5023519088 @default.
- W2921568354 creator A5023826377 @default.
- W2921568354 creator A5033576562 @default.
- W2921568354 creator A5041018881 @default.
- W2921568354 creator A5056474918 @default.
- W2921568354 creator A5057193669 @default.
- W2921568354 creator A5067183847 @default.
- W2921568354 creator A5072681016 @default.
- W2921568354 date "2019-03-06" @default.
- W2921568354 modified "2023-10-17" @default.
- W2921568354 title "Aluminum Hydroxide Secondary Building Units in a Metal–Organic Framework Support Earth-Abundant Metal Catalysts for Broad-Scope Organic Transformations" @default.
- W2921568354 cites W1852140041 @default.
- W2921568354 cites W1902427796 @default.
- W2921568354 cites W1978890358 @default.
- W2921568354 cites W1982620794 @default.
- W2921568354 cites W1993420947 @default.
- W2921568354 cites W1999827317 @default.
- W2921568354 cites W2004550299 @default.
- W2921568354 cites W2004867175 @default.
- W2921568354 cites W2004952068 @default.
- W2921568354 cites W2005594390 @default.
- W2921568354 cites W2005767625 @default.
- W2921568354 cites W2020769232 @default.
- W2921568354 cites W2023692017 @default.
- W2921568354 cites W2032723861 @default.
- W2921568354 cites W2042618608 @default.
- W2921568354 cites W2043562330 @default.
- W2921568354 cites W2046753449 @default.
- W2921568354 cites W2051191132 @default.
- W2921568354 cites W2053286705 @default.
- W2921568354 cites W2055418060 @default.
- W2921568354 cites W2061566121 @default.
- W2921568354 cites W2063764657 @default.
- W2921568354 cites W2072436367 @default.
- W2921568354 cites W2072772146 @default.
- W2921568354 cites W2080326204 @default.
- W2921568354 cites W2080350898 @default.
- W2921568354 cites W2081890623 @default.
- W2921568354 cites W2082507193 @default.
- W2921568354 cites W2083720874 @default.
- W2921568354 cites W2084311144 @default.
- W2921568354 cites W2089290475 @default.
- W2921568354 cites W2105120330 @default.
- W2921568354 cites W2110921739 @default.
- W2921568354 cites W2111118274 @default.
- W2921568354 cites W2115764422 @default.
- W2921568354 cites W2116829659 @default.
- W2921568354 cites W2124077044 @default.
- W2921568354 cites W2126676230 @default.
- W2921568354 cites W2133853647 @default.
- W2921568354 cites W2135059442 @default.
- W2921568354 cites W2135438801 @default.
- W2921568354 cites W2141939342 @default.
- W2921568354 cites W2159326564 @default.
- W2921568354 cites W2159466701 @default.
- W2921568354 cites W2165591701 @default.
- W2921568354 cites W2276866860 @default.
- W2921568354 cites W2302156710 @default.
- W2921568354 cites W2312196733 @default.
- W2921568354 cites W2313559141 @default.
- W2921568354 cites W2314999739 @default.
- W2921568354 cites W2317020669 @default.
- W2921568354 cites W2321357295 @default.
- W2921568354 cites W2321972710 @default.
- W2921568354 cites W2327019704 @default.
- W2921568354 cites W2329766173 @default.
- W2921568354 cites W2330227554 @default.
- W2921568354 cites W2330458018 @default.
- W2921568354 cites W2331001885 @default.
- W2921568354 cites W2335481966 @default.
- W2921568354 cites W2412087944 @default.
- W2921568354 cites W2418077897 @default.
- W2921568354 cites W2461801429 @default.
- W2921568354 cites W2462422652 @default.
- W2921568354 cites W2477343743 @default.
- W2921568354 cites W2490455750 @default.
- W2921568354 cites W2513328261 @default.
- W2921568354 cites W2548630764 @default.
- W2921568354 cites W2556752910 @default.
- W2921568354 cites W2562044353 @default.
- W2921568354 cites W2569012662 @default.
- W2921568354 cites W2586186814 @default.
- W2921568354 cites W2610738004 @default.
- W2921568354 cites W2611215890 @default.
- W2921568354 cites W2743881703 @default.
- W2921568354 cites W2750322300 @default.
- W2921568354 cites W2765734032 @default.
- W2921568354 cites W2772899329 @default.
- W2921568354 cites W2791915426 @default.
- W2921568354 cites W2806810327 @default.
- W2921568354 cites W2911972538 @default.
- W2921568354 cites W2951685583 @default.
- W2921568354 cites W2953122546 @default.
- W2921568354 cites W4239107519 @default.
- W2921568354 cites W4248080714 @default.