Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature
Abstract
Developing homogeneous catalysts that convert CS2 and COS pollutants into environmentally benign products is important for both fundamental catalytic research and applied environmental science. Here we report a series of air-stable dimeric Pd complexes that mediate the facile hydrolytic cleavage of both CS2 carbon–sulfur bonds at 25 °C to produce CO2 and trimeric Pd complexes. Oxidation of the trimeric complexes with HNO3 regenerates the dimeric starting complexes with the release of SO2 and NO2. Isotopic labelling confirms that the carbon and oxygen atoms of CO2 originate from CS2 and H2O, respectively, and reaction intermediates were observed by gas-phase and electrospray ionization mass spectrometry, as well as by Fourier transform infrared spectroscopy. We also propose a plausible mechanistic scenario based on the experimentally observed intermediates. Here, the mechanism involves intramolecular attack by a nucleophilic Pd–OH moiety on the carbon atom of coordinated µ-OCS2, which on deprotonation cleaves one C–S bond and simultaneously forms a C–O bond. Coupled C–S cleavage and CO2 release to yield [(bpy)3Pd3(µ3-S)2](NO3)2 (bpy, 2,2'-bipyridine) provides the thermodynamic driving force for the reaction.
- Authors:
-
- Beijing Univ. of Technology (China); Univ. of Chinese Academy of Sciences, Beijing (China)
- Univ. of Chinese Academy of Sciences, Beijing (China)
- Zhejiang Univ., Hangzhou (China)
- Northwestern Univ., Evanston, IL (United States)
- Beijing Univ. of Technology (China)
- Renmin Univ. of China, Beijing (China)
- Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Lemont, IL (United States)
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC); Beijing Natural Science Foundation; National Science Foundation (NSF)
- OSTI Identifier:
- 1871007
- Grant/Contract Number:
- FG02-03ER15457; 21471011; 21574135; 91127039; 51303180; 21203245; 21532005; 21327010; 2162043; CHE-1464488
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Nature Chemistry
- Additional Journal Information:
- Journal Volume: 9; Journal Issue: 2; Journal ID: ISSN 1755-4330
- Publisher:
- Nature Publishing Group
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental monitoring; Solid-state chemistry
Citation Formats
Jiang, Xuan-Feng, Huang, Hui, Chai, Yun-Feng, Lohr, Tracy Lynn, Yu, Shu-Yan, Lai, Wenzhen, Pan, Yuan-Jiang, Delferro, Massimiliano, and Marks, Tobin J. Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature. United States: N. p., 2016.
Web. doi:10.1038/nchem.2637.
Jiang, Xuan-Feng, Huang, Hui, Chai, Yun-Feng, Lohr, Tracy Lynn, Yu, Shu-Yan, Lai, Wenzhen, Pan, Yuan-Jiang, Delferro, Massimiliano, & Marks, Tobin J. Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature. United States. https://doi.org/10.1038/nchem.2637
Jiang, Xuan-Feng, Huang, Hui, Chai, Yun-Feng, Lohr, Tracy Lynn, Yu, Shu-Yan, Lai, Wenzhen, Pan, Yuan-Jiang, Delferro, Massimiliano, and Marks, Tobin J. Mon .
"Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature". United States. https://doi.org/10.1038/nchem.2637. https://www.osti.gov/servlets/purl/1871007.
@article{osti_1871007,
title = {Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature},
author = {Jiang, Xuan-Feng and Huang, Hui and Chai, Yun-Feng and Lohr, Tracy Lynn and Yu, Shu-Yan and Lai, Wenzhen and Pan, Yuan-Jiang and Delferro, Massimiliano and Marks, Tobin J.},
abstractNote = {Developing homogeneous catalysts that convert CS2 and COS pollutants into environmentally benign products is important for both fundamental catalytic research and applied environmental science. Here we report a series of air-stable dimeric Pd complexes that mediate the facile hydrolytic cleavage of both CS2 carbon–sulfur bonds at 25 °C to produce CO2 and trimeric Pd complexes. Oxidation of the trimeric complexes with HNO3 regenerates the dimeric starting complexes with the release of SO2 and NO2. Isotopic labelling confirms that the carbon and oxygen atoms of CO2 originate from CS2 and H2O, respectively, and reaction intermediates were observed by gas-phase and electrospray ionization mass spectrometry, as well as by Fourier transform infrared spectroscopy. We also propose a plausible mechanistic scenario based on the experimentally observed intermediates. Here, the mechanism involves intramolecular attack by a nucleophilic Pd–OH moiety on the carbon atom of coordinated µ-OCS2, which on deprotonation cleaves one C–S bond and simultaneously forms a C–O bond. Coupled C–S cleavage and CO2 release to yield [(bpy)3Pd3(µ3-S)2](NO3)2 (bpy, 2,2'-bipyridine) provides the thermodynamic driving force for the reaction.},
doi = {10.1038/nchem.2637},
journal = {Nature Chemistry},
number = 2,
volume = 9,
place = {United States},
year = {Mon Oct 24 00:00:00 EDT 2016},
month = {Mon Oct 24 00:00:00 EDT 2016}
}
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