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Title: Templating metastable Pd 2 carboxylate aggregates

Abstract

Evaluation of the potential for metal–metal (M–M) cooperation to enable catalysis requires access to specific polynuclear aggregates that display appropriate geometry and size. In many cases, exerting synthetic control over the aggregation of simple metal salts is a challenge. For example, Pd(II) acetate self assembles as a trimer (i.e. Pd3(OAc)6) both in the solid state and in solution and does not feature close Pd–Pd interactions. Related carboxylate-supported Pd2 aggregates (i.e. Pd2(OAc)4), which would feature close Pd–Pd interactions, are thermodynamically metastable in solution phase and thus largely unavailable. Here we demonstrate ion metathesis within pre-formed metal–organic frameworks (MOFs) to prepare metastable Pd2 tetracarboxylates sites. The newly synthesized materials are characterized by elemental analysis, PXRD, SCXRD, EXAFS, XANES, and gas adsorption analysis. In addition, the critical role of network solvation on the kinetics of ion metathesis was revealed by coupled TGA-MS and ICP-MS experiments. The demonstration of templated ion metathesis to generate specific metastable coordination sites that are inaccessible in solution phase chemistry represents a new opportunity to interrogate the chemistry of specific polynuclear metal aggregates.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Texas A&M University, Department of Chemistry, College Station, USA
  2. DND-CAT, Northwestern Synchrotron Research Centre at the Advanced Photon Source, Argonne, USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); Welch Foundation
OSTI Identifier:
1485518
Alternate Identifier(s):
OSTI ID: 1497104
Grant/Contract Number:  
SC0018977; AC02-06CH11357; CHE-1346572; A-1907
Resource Type:
Journal Article: Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 10 Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Wang, Chen-Hao, Gao, Wen-Yang, Ma, Qing, and Powers, David C. Templating metastable Pd 2 carboxylate aggregates. United Kingdom: N. p., 2019. Web. doi:10.1039/C8SC04940H.
Wang, Chen-Hao, Gao, Wen-Yang, Ma, Qing, & Powers, David C. Templating metastable Pd 2 carboxylate aggregates. United Kingdom. https://doi.org/10.1039/C8SC04940H
Wang, Chen-Hao, Gao, Wen-Yang, Ma, Qing, and Powers, David C. 2019. "Templating metastable Pd 2 carboxylate aggregates". United Kingdom. https://doi.org/10.1039/C8SC04940H.
@article{osti_1485518,
title = {Templating metastable Pd 2 carboxylate aggregates},
author = {Wang, Chen-Hao and Gao, Wen-Yang and Ma, Qing and Powers, David C.},
abstractNote = {Evaluation of the potential for metal–metal (M–M) cooperation to enable catalysis requires access to specific polynuclear aggregates that display appropriate geometry and size. In many cases, exerting synthetic control over the aggregation of simple metal salts is a challenge. For example, Pd(II) acetate self assembles as a trimer (i.e. Pd3(OAc)6) both in the solid state and in solution and does not feature close Pd–Pd interactions. Related carboxylate-supported Pd2 aggregates (i.e. Pd2(OAc)4), which would feature close Pd–Pd interactions, are thermodynamically metastable in solution phase and thus largely unavailable. Here we demonstrate ion metathesis within pre-formed metal–organic frameworks (MOFs) to prepare metastable Pd2 tetracarboxylates sites. The newly synthesized materials are characterized by elemental analysis, PXRD, SCXRD, EXAFS, XANES, and gas adsorption analysis. In addition, the critical role of network solvation on the kinetics of ion metathesis was revealed by coupled TGA-MS and ICP-MS experiments. The demonstration of templated ion metathesis to generate specific metastable coordination sites that are inaccessible in solution phase chemistry represents a new opportunity to interrogate the chemistry of specific polynuclear metal aggregates.},
doi = {10.1039/C8SC04940H},
url = {https://www.osti.gov/biblio/1485518}, journal = {Chemical Science},
issn = {2041-6520},
number = 6,
volume = 10,
place = {United Kingdom},
year = {Wed Feb 06 00:00:00 EST 2019},
month = {Wed Feb 06 00:00:00 EST 2019}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at https://doi.org/10.1039/C8SC04940H

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Cited by: 10 works
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