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Title: A Hafnium-Based Metal–Organic Framework as a Nature-Inspired Tandem Reaction Catalyst

Abstract

Tandem catalytic systems, often inspired by biological systems, offer many advantages in the formation of highly functionalized small molecules. Herein, a new MOF with porphyrinic struts and Hf6 nodes is reported. This MOF demonstrates catalytic efficacy in the tandem oxidation and functionalization of styrene utilizing molecular oxygen as a terminal oxidant. The product, a protected 1,2-aminoalcohol, is formed selectively and with high efficiency using this recyclable heterogeneous catalyst. Significantly, the unusual regioselective transformation occurs only when a Fe-decorated Hf6-node and the Fe-porphyrin strut work in concert. This report is an example of concurrent orthogonal tandem catalysis.

Authors:
 [1];  [1];  [1];  [2];  [2];  [1];  [3];  [4];  [1];  [1];  [5];  [4];  [1];  [2];  [1];  [6]
  1. International Institute for Nanotechnology (IIN) and Center for the Chemistry of Integrated Systems (CCIS), Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States
  2. Department of Chemistry, Chemical Theory Center, and Supercomputing Institute, University of Minnesota, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States
  3. Chemical Science and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States
  4. X-ray Science Division, Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States
  5. Chemical Science and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, Illinois 60439, United States; School of Chemical Engineering, Purdue University, 480 Stadium Mall Drive, West Lafayette, Indiana 47906, United States
  6. International Institute for Nanotechnology (IIN) and Center for the Chemistry of Integrated Systems (CCIS), Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, Illinois 60208, United States; Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 22254, Saudi Arabia
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1392408
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 137; Journal Issue: 42; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
Hf-MOFs; MOF Catalysis; Zr-MOFs; metal organic frameworks; porphyrinic; post-synthesis modification

Citation Formats

Beyzavi, M. Hassan, Vermeulen, Nicolaas A., Howarth, Ashlee J., Tussupbayev, Samat, League, Aaron B., Schweitzer, Neil M., Gallagher, James R., Platero-Prats, Ana E., Hafezi, Nema, Sarjeant, Amy A., Miller, Jeffrey T., Chapman, Karena W., Stoddart, J. Fraser, Cramer, Christopher J., Hupp, Joseph T., and Farha, Omar K. A Hafnium-Based Metal–Organic Framework as a Nature-Inspired Tandem Reaction Catalyst. United States: N. p., 2015. Web. doi:10.1021/jacs.5b08440.
Beyzavi, M. Hassan, Vermeulen, Nicolaas A., Howarth, Ashlee J., Tussupbayev, Samat, League, Aaron B., Schweitzer, Neil M., Gallagher, James R., Platero-Prats, Ana E., Hafezi, Nema, Sarjeant, Amy A., Miller, Jeffrey T., Chapman, Karena W., Stoddart, J. Fraser, Cramer, Christopher J., Hupp, Joseph T., & Farha, Omar K. A Hafnium-Based Metal–Organic Framework as a Nature-Inspired Tandem Reaction Catalyst. United States. https://doi.org/10.1021/jacs.5b08440
Beyzavi, M. Hassan, Vermeulen, Nicolaas A., Howarth, Ashlee J., Tussupbayev, Samat, League, Aaron B., Schweitzer, Neil M., Gallagher, James R., Platero-Prats, Ana E., Hafezi, Nema, Sarjeant, Amy A., Miller, Jeffrey T., Chapman, Karena W., Stoddart, J. Fraser, Cramer, Christopher J., Hupp, Joseph T., and Farha, Omar K. 2015. "A Hafnium-Based Metal–Organic Framework as a Nature-Inspired Tandem Reaction Catalyst". United States. https://doi.org/10.1021/jacs.5b08440.
@article{osti_1392408,
title = {A Hafnium-Based Metal–Organic Framework as a Nature-Inspired Tandem Reaction Catalyst},
author = {Beyzavi, M. Hassan and Vermeulen, Nicolaas A. and Howarth, Ashlee J. and Tussupbayev, Samat and League, Aaron B. and Schweitzer, Neil M. and Gallagher, James R. and Platero-Prats, Ana E. and Hafezi, Nema and Sarjeant, Amy A. and Miller, Jeffrey T. and Chapman, Karena W. and Stoddart, J. Fraser and Cramer, Christopher J. and Hupp, Joseph T. and Farha, Omar K.},
abstractNote = {Tandem catalytic systems, often inspired by biological systems, offer many advantages in the formation of highly functionalized small molecules. Herein, a new MOF with porphyrinic struts and Hf6 nodes is reported. This MOF demonstrates catalytic efficacy in the tandem oxidation and functionalization of styrene utilizing molecular oxygen as a terminal oxidant. The product, a protected 1,2-aminoalcohol, is formed selectively and with high efficiency using this recyclable heterogeneous catalyst. Significantly, the unusual regioselective transformation occurs only when a Fe-decorated Hf6-node and the Fe-porphyrin strut work in concert. This report is an example of concurrent orthogonal tandem catalysis.},
doi = {10.1021/jacs.5b08440},
url = {https://www.osti.gov/biblio/1392408}, journal = {Journal of the American Chemical Society},
issn = {0002-7863},
number = 42,
volume = 137,
place = {United States},
year = {Thu Oct 15 00:00:00 EDT 2015},
month = {Thu Oct 15 00:00:00 EDT 2015}
}