Please use this identifier to cite or link to this item: http://hdl.handle.net/2440/128438
Citations
Scopus Web of Science® Altmetric
?
?
Type: Journal article
Title: Highly active gas phase organometallic catalysis supported within metal-organic framework pores
Author: Peralta, R.A.
Huxley, M.T.
Evans, J.D.
Fallon, T.
Cao, H.
He, M.
Zhao, X.S.
Agnoli, S.
Sumby, C.J.
Doonan, C.J.
Citation: Journal of the American Chemical Society, 2020; 142(31):13533-13543
Publisher: ACS Publications
Issue Date: 2020
ISSN: 0002-7863
1520-5126
Statement of
Responsibility: 
Ricardo A. Peralta, Michael T. Huxley, Jack D. Evans, Thomas Fallon, Haijie Cao, Maoxia He ... et al.
Abstract: Metal-organic frameworks (MOFs) can act as a platform for the heterogenization of molecular catalysts, providing improved stability, allowing easy catalyst recovery and a route toward structural elucidation of the active catalyst. We have developed a MOF, 1, possessing vacant N,N-chelating sites which are accessible via the porous channels that penetrate the structure. In the present work, cationic rhodium(I) norbornadiene (NBD) and bis(ethylene) (ETH) complexes paired with both noncoordinating and coordinating anions have been incorporated into the N,N-chelation sites of 1 via postsynthetic metalation and facile anion exchange. Exploiting the crystallinity of the host framework, the immobilized Rh(I) complexes were structurally characterized using X-ray crystallography. Ethylene hydrogenation catalysis by 1·[Rh(NBD)]X and 1·[Rh(ETH)2]X (X = Cl and BF4) was studied in the gas phase (2 bar, 46 °C) to reveal that 1·[Rh(ETH)2](BF4) was the most active catalyst (TOF = 64 h-1); the NBD materials and the chloride salt were notably less active. On the basis of these observations, the activity of the Rh(I) bis(ethylene) complexes, 1·[Rh(ETH)2]BF4 and 1·[Rh(ETH)2]Cl, in butene isomerization was also studied using gas-phase NMR spectroscopy. Under one bar of butene at 46 °C, 1·[Rh(ETH)2]BF4 rapidly catalyzes the conversion of 1-butene to 2-butene with a TOF averaging 2000 h-1 over five cycles. Notably, the chloride derivative, 1 [Rh(ETH)2]Cl displays negligible activity in comparison. XPS analysis of the postcatalysis sample, supported by DFT calculations, suggest that the catalytic activity is inhibited by the strong interactions between a Rh(III) allyl hydride intermediate and the chloride anion.
Rights: Copyright © 2020 American Chemical Society
RMID: 1000023791
DOI: 10.1021/jacs.0c05286
Grant ID: http://purl.org/au-research/grants/arc/DP160103234
http://purl.org/au-research/grants/arc/DP190101402
http://purl.org/au-research/grants/arc/FL170100101
Appears in Collections:Chemistry and Physics publications

Files in This Item:
There are no files associated with this item.


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.