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Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration

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Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration Chemistry Publications Chemistry 11-4-2015 Mesoporous Silica-Supported Amidozirconium- Catalyzed Carbonyl Hydroboration Naresh Eedugurala Iowa State University, [email protected] Zhuoran Wang Iowa State University, [email protected] Umesh Chaudhary Iowa State University, [email protected] Nicholas C. Nelson Iowa State University, [email protected] Kapil Kandel Iowa State University, [email protected] See next page for additional authors Follow this and additional works at: http://lib.dr.iastate.edu/chem_pubs Part of the Chemistry Commons The ompc lete bibliographic information for this item can be found at http://lib.dr.iastate.edu/ chem_pubs/225. For information on how to cite this item, please visit http://lib.dr.iastate.edu/ howtocite.html. This Article is brought to you for free and open access by the Chemistry at Iowa State University Digital Repository. It has been accepted for inclusion in Chemistry Publications by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration Abstract The yh droboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid-state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily ≡SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr(NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane ≡SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1H/2H and 11B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. Thus, these supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites. Keywords single-site catalysts, carbonyl hydroboration, zirconium hydride, interfacial catalysis, mesoporous silica, solid- state NMR Disciplines Chemistry Comments Reprinted (adapted) with permission from ACS Catalysis 5 (2015): 7399, doi: 10.1021/acscatal.5b01671. Copyright 2015 American Chemical Society. Authors Naresh Eedugurala, Zhuoran Wang, Umesh Chaudhary, Nicholas C. Nelson, Kapil Kandel, Takeshi Kobayashi, Igor I. Slowing, Marek Pruski, and Aaron D. Sadow This article is available at Iowa State University Digital Repository: http://lib.dr.iastate.edu/chem_pubs/225 Research Article pubs.acs.org/acscatalysis Mesoporous Silica-Supported Amidozirconium-Catalyzed Carbonyl Hydroboration ‡ Naresh Eedugurala, Zhuoran Wang, Umesh Chaudhary, Nicholas Nelson, Kapil Kandel, Takeshi Kobayashi, Igor I. Slowing, Marek Pruski,* and Aaron D. Sadow* U.S. Department of Energy Ames Laboratory and Department of Chemistry, Iowa State University, 1605 Gilman Hall, Ames, Iowa 50011, United States *S Supporting Information ABSTRACT: The hydroboration of aldehydes and ketones using a silica-supported zirconium catalyst is reported. Reaction of Zr(NMe2)4 and mesoporous silica nanoparticles (MSN) provides the catalytic material Zr(NMe2)n@MSN. Exhaustive characterization of Zr(NMe2)n@MSN with solid- state (SS)NMR and infrared spectroscopy, as well as through reactivity studies, suggests its surface structure is primarily SiOZr(NMe2)3. The presence of these nitrogen-containing zirconium sites is supported by 15N NMR spectroscopy, including natural abundance 15N NMR measurements using dynamic nuclear polarization (DNP) SSNMR. The Zr- (NMe2)n@MSN material reacts with pinacolborane (HBpin) to provide Me2NBpin and the material ZrH/Bpin@MSN that is composed of interacting surface-bonded zirconium hydride and surface-bonded borane SiOBpin moieties in an approximately 1:1 ratio, as well as zirconium sites coordinated by dimethylamine. The ZrH/Bpin@MSN is characterized by 1 2 11 H/ H and B SSNMR and infrared spectroscopy and through its reactivity with D2. The zirconium hydride material or the zirconium amide precursor Zr(NMe2)n@MSN catalyzes the selective hydroboration of aldehydes and ketones with HBpin in the presence of functional groups that are often reduced under hydroboration conditions or are sensitive to metal hydrides, including olefins, alkynes, nitro groups, halides, and ethers. Remarkably, this catalytic material may be recycled without loss of activity at least eight times, and air-exposed materials are catalytically active. Thus, these supported zirconium centers are robust catalytic sites for carbonyl reduction and that surface-supported, catalytically reactive zirconium hydride may be generated from zirconium-amide or zirconium alkoxide sites. KEYWORDS: single-site catalysts, carbonyl hydroboration, zirconium hydride, interfacial catalysis, mesoporous silica, solid-state NMR ■ INTRODUCTION versions as well as a straightforward means for recycling the 1,2 catalytic materials. Surface-supported early-transition-metal hydrides are highly We recently reported a homogeneous magnesium-catalyzed reactive toward C−H bond breaking reactions that allow 3 cleavage and hydroboration of esters using an in situ generated stoichiometric methane metalation and catalytic conversions 24 fi 4 5 magnesium hydridoborate catalyst. Despite the oxophilicity of such as ole npolymerization, hydrogenation, H/D ex- the magnesium center, the catalytic site could be generated by change,6 alkane metathesis, and hydrogenolysis of polyethylene − reaction of pinacolborane (HBpin) and magnesium alkoxide. and other alkanes.7 10 Although the surface provides kinetic Similarly, [{Nacnac}MgH]2 (Nacnac = ((2,6-iPr2C6H3)- stabilization of metal hydrides against multimetallic decom- NCMe)2HC) is a highly active catalyst for hydroboration of position reactions, solution-phase early-metal and rare-earth pyridines, ketones, and aldehydes.22,25 A related zwitterionic hydrides are implicated in a range of catalytic chemistry ffi − magnesium catalyst is su ciently reactive to reduce carbon including hydrosilylation,11 17 hydrogenation,18 dehydrocou- 26 − dioxide to a methanol equivalent. Hydroboration of aldehydes pling and dehydrogenative polymerization,19 21 and hydro- and ketones is catalyzed by soluble titanium,27 molybdenum,28 boration.22,23 Often, the metal hydrides in these reactions are as well as a few late metal catalysts.29,30 Recently, divalent generated and used in situ or are proposed as intermediates in germanium and tin compounds were also shown to catalyze this catalytic cycles. This in situ generation could also be an reaction, and hydrides were postulated intermediates.31 Group advantageous approach for the application of surface-supported 4-catalyzed carbonyl hydrosilylations and hydrogenations are metal hydrides in catalysis. Moreover, a surface-supported hydride such as ( SiO)3ZrH could tolerate harsher conditions Received: July 31, 2015 (e.g., higher temperature) than soluble analogues in catalytic Revised: October 29, 2015 addition chemistry, thereby permitting more difficult con- © XXXX American Chemical Society 7399 DOI: 10.1021/acscatal.5b01671 ACS Catal. 2015, 5, 7399−7414 ACS Catalysis Research Article 11,32−35 ’ 1 also known, and although Schwartz s reagent catalyzes N2 sorption/desorption, powder XRD, TEM, solid-state H, hydroboration of alkynes,36 we are not aware of previous 2H, 11B, 13C, and 15N SSNMR spectroscopy, 15N SSNMR reports of zirconium-catalyzed hydroboration of carbonyls. In spectroscopy enhanced by dynamic nuclear polarization 45 addition, the reaction of Zr(NMe2)4 and SBA-15 was recently (DNP), and infrared spectroscopy. Zr(NMe2)4, {PhB- 37 Me2 Me2 reported to give an azazirconocyclopropane surface species, as (Ox )2C5H4}Zr(NMe2)2 (Ox = 4,4-dimethyl-2-oxazo- 38 46 47,48 49 does a titanium amide on silica en route to a titanium imido. line), Si(SiMe3)4, and DBpin were synthesized Notably, the azazirconocyclopropane species reacts with according to literature procedures. Pinacolborane (used as hydrogen to give a zirconium hydride that catalyzes hydro- received) and 98% 15N-labeled [H 15NMe ]Cl (dried under fi 39 − − 2 2 genation of ole ns. The catalytic C H and C C bond- vacuum at 120 °C for 2 h) were purchased from Aldrich. breaking and -forming reactions of surface-supported zirconium Solution-phase 1H, 13C{1H} and 11B NMR spectra were hydride are notoriously sensitive to oxygen-containing collected either on a Bruker DRX 400 MHz spectrometer, impurities, which give irreversible deactivation of the catalytic Bruker Avance III 600 MHz spectrometer or a Varian MR 400 sites. MHz spectrometer.
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