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Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature

Nature Chemistry volume 9, pages 188–193 (2017)Cite this article

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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. 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.

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Figure 1: Converting CS2 into CO2 using dimeric palladium complexes in water.
Figure 2: Monitoring the reaction of CS2 with 0.05 M aqueous 2a·2NO3 by ESI–MS as a function of time.
Figure 3: Proposed mechanism for the reaction of 2a2+ with CS2 from DFT calculations.

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Acknowledgements

This research was supported by National Natural Science Foundation of China (Grant numbers 21471011, 21574135, 91127039, 51303180, 21203245, 21532005, 21327010), the Beijing Natural Science Foundation (Grant 2162043), the One Hundred Talents Program, the Chinese Academy of Sciences, the Importation and Development of High-Caliber Talents Project of the Beijing Municipal Institution and Beijing Postdoctoral Research Foundation (Grant 2015M570017) and the Beijing Synchrotron Radiation Facility for crystal structure determination using synchrotron radiation X-ray diffraction analysis. We also thank H. Ma (Beijing Institute of Technology) for the X-ray crystallography. Research at Northwestern University is supported by the US National Science Foundation under grant CHE-1464488. The Northwestern CleanCat Core Facility acknowledges funding from the US Department of Energy (Grant DE-FG02-03ER15457) used for the purchase of the portable universal gas analyser. We thank N. M. Schweitzer for supporting the mass spectroscopy.

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Author notes

  1. Massimiliano Delferro

    Present address: Present address: Chemical Sciences and Engineering Division, Argonne National Laboratory, Lemont, Illinois 60439, USA,

Authors and Affiliations

  1. Department of Chemistry and Chemical Industry, Beijing Key Laboratory for Green Catalysis and Separation, Laboratory for Self-Assembly Chemistry, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing, 100124, China

    Xuan-Feng Jiang & Shu-Yan Yu

  2. College of Materials Science and Opto-electronic Technology and Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing, 100049, China

    Xuan-Feng Jiang & Hui Huang

  3. Department of Chemistry, Zhejiang University, Hangzhou, 310027, China

    Yun-Feng Chai & Yuan-Jiang Pan

  4. Department of Chemistry and the Center for Surface Science and Catalysis, Northwestern University, Evanston, 60208, Illinois, USA

    Tracy Lynn Lohr, Massimiliano Delferro & Tobin J. Marks

  5. Department of Chemistry, Renmin University of China, Beijing, 100872, China

    Wenzhen Lai

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Contributions

S.-Y.Y. and H.H. conceived the study. H.H., S.-Y.Y., M.D., T.L.L. and T.J. M. planned the research. X.-F.J., H.H. and T.L.L. synthesized and characterized the compounds. Y.-J.P. and Y.-F.C conducted the on-line ESI experiments and analysis. W.L. conducted the DFT calculations. H.H., X.-F.J., T.L.L., S.-Y.Y., W.L., M.D. and T.J.M. prepared the manuscript. All the authors commented on the manuscript.

Corresponding authors

Correspondence to Hui Huang, Shu-Yan Yu, Wenzhen Lai, Yuan-Jiang Pan, Massimiliano Delferro or Tobin J. Marks.

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The authors declare no competing financial interests.

Supplementary information

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Supplementary information (PDF 2558 kb)

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Crystallographic data for compound 1a (CIF 3029 kb)

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Crystallographic data for compound 2b (CIF 225 kb)

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Crystallographic data for compound 3a (CIF 5348 kb)

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Crystallographic data for compound 3b (CIF 3309 kb)

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Jiang, XF., Huang, H., Chai, YF. et al. Hydrolytic cleavage of both CS2 carbon–sulfur bonds by multinuclear Pd(II) complexes at room temperature. Nature Chem 9, 188–193 (2017). https://doi.org/10.1038/nchem.2637

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