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Title: Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal-free Hydrogenation of Alkenes

Authors:
ORCiD logo [1];  [1];  [2];  [3];  [3]; ORCiD logo [1]; ORCiD logo [4]
  1. Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2 52074 Aachen Germany
  2. Department of Chemistry & Biochemistry, University of California, Santa Barbara CA 93106 USA
  3. Department of Chemistry & Biochemistry, University of California, Santa Barbara CA 93106 USA, Department of Chemical Engineering, University of California, Santa Barbara CA 93106 USA
  4. Institut für Technische und Makromolekulare Chemie, RWTH Aachen University, Worringerweg 2 52074 Aachen Germany, Ernst-Berl-Institut, Technische Chemie II, Technische Universität Darmstadt, Alarich-Weiss-Straße 8 64287 Darmstadt Germany
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1420002
Grant/Contract Number:
FG-02-03ER15467
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
ChemCatChem
Additional Journal Information:
Related Information: CHORUS Timestamp: 2018-02-09 04:40:34; Journal ID: ISSN 1867-3880
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Willms, Andrea, Schumacher, Hannah, Tabassum, Tarnuma, Qi, Long, Scott, Susannah L., Hausoul, Peter J. C., and Rose, Marcus. Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal-free Hydrogenation of Alkenes. Germany: N. p., 2018. Web. doi:10.1002/cctc.201701783.
Willms, Andrea, Schumacher, Hannah, Tabassum, Tarnuma, Qi, Long, Scott, Susannah L., Hausoul, Peter J. C., & Rose, Marcus. Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal-free Hydrogenation of Alkenes. Germany. doi:10.1002/cctc.201701783.
Willms, Andrea, Schumacher, Hannah, Tabassum, Tarnuma, Qi, Long, Scott, Susannah L., Hausoul, Peter J. C., and Rose, Marcus. 2018. "Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal-free Hydrogenation of Alkenes". Germany. doi:10.1002/cctc.201701783.
@article{osti_1420002,
title = {Solid Molecular Frustrated Lewis Pairs in a Polyamine Organic Framework for the Catalytic Metal-free Hydrogenation of Alkenes},
author = {Willms, Andrea and Schumacher, Hannah and Tabassum, Tarnuma and Qi, Long and Scott, Susannah L. and Hausoul, Peter J. C. and Rose, Marcus},
abstractNote = {},
doi = {10.1002/cctc.201701783},
journal = {ChemCatChem},
number = ,
volume = ,
place = {Germany},
year = 2018,
month = 2
}

Journal Article:
Free Publicly Available Full Text
This content will become publicly available on February 9, 2019
Publisher's Accepted Manuscript

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  • 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 M 82-O) 82-OH) 4 and octahedral M6(μ 3-O) 43-OH) 4. While the M 6-SBU is isostructural with the 12-connected octahedral SBUs of UiO-type MOFs, the M 8-SBU is composed of eight MIV ions in a cubic fashion linked by eight μ 2-oxo and four μ 2-OH groups. The metalation of Zr-MTBC SBUs with CoCl 2, followed by treatment with NaBEt 3H, afforded highlymore » 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 Zr 8-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.« less
  • Anisotropic interactions present in three new nitroxide radicals prepared by N,N addition of NO to various borane-phosphane frustrated Lewis pairs (FLPs) have been characterized by continuous-wave (cw) and pulsed X-band EPR spectroscopies in solid FLP-hydroxylamine matrices at 100 K. Anisotropic g-tensor values and {sup 11}B, {sup 14}N, and {sup 31}P hyperfine coupling tensor components have been extracted from continuous-wave lineshape analyses, electron spin echo envelope modulation (ESEEM), and hyperfine sublevel correlation spectroscopy (HYSCORE) experiments with the help of computer simulation techniques. Suitable fitting constraints are developed on the basis of density functional theory (DFT) calculations. These calculations reveal that differentmore » from the situation in standard nitroxide radicals (TEMPO), the g-tensors are non-coincident with any of the nuclear hyperfine interaction tensors. The determination of these interaction parameters turns out to be successful, as the cw- and pulse EPR experiments are highly complementary in informational content. While the continuous-wave lineshape is largely influenced by the anisotropic hyperfine coupling to {sup 14}N and {sup 31}P, the ESEEM and HYSCORE spectra contain important information about the {sup 11}B hyperfine coupling and nuclear electric quadrupolar interaction. The set of cw- and pulsed EPR experiments, with fitting constraints developed by DFT calculations, defines an efficient strategy for the structural analysis of paramagnetic FLP adducts.« less
  • Reaction of solid ((Ph{sub 3}P){sub 2}Ir(C{sub 8}H{sub 12})){sub 3}PW{sub 12}O{sub 40} with D{sub 2} gas produces cyclooctane containing up to 16 deuterium atoms. The c-C{sub 8}D{sub n}H{sub 16-n} isotopomer distribution is analyzed by Poisson statistics and interpreted in terms of C-H activation involving Ir-D-C-H exchange in an intermediate species containing coordinated cyclooctene. The results are compared with those from D{sub 2} reduction of ((Ph{sub 3}P){sub 2}Ir(C{sub 8}H{sub 12}))(PF{sub 6}) in the solid state and in acetone solution, in which cases, an additional exchange process operates. Solid-state {sup 2}H NMR shows that, even at low temperatures, small organic molecules such asmore » cyclooctane and benzene undergo nearly isotropic motion.« less
  • Here, we describe a new strategy to generate non-coordinating anions using zwitterionic metal–organic frameworks (MOFs). By assembly of anionic inorganic secondary building blocks (SBUs) ([In(CO 2) 4] $-$) with cationic metalloporphyrin-based organic linkers, we prepared zwitterionic MOFs in which the complete internal charge separation effectively prevents the potential binding of the counteranion to the cationic metal center. We demonstrate the enhanced Lewis acidity of Mn III- and Fe III-porphyrins in the zwitterionic MOFs in three representative electrocyclization reactions: [2 + 1] cycloisomerization of enynes, [3 + 2] cycloaddition of aziridines and alkenes, and [4 + 2] hetero-Diels–Alder cycloaddition of aldehydesmore » with dienes. Lastly, this work paves a new way to design functional MOFs for tunable chemical catalysis.« less