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

Xuan Feng Jiang, Hui Huang, Yun Feng Chai, Tracy Lynn Lohr, Shu Yan Yu, Wenzhen Lai, Yuan Jiang Pan, Massimiliano Delferro, Tobin J Marks

Research output: Contribution to journalArticle

24 Citations (Scopus)

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.

Original languageEnglish
Pages (from-to)188-193
Number of pages6
JournalNature Chemistry
Volume9
Issue number2
DOIs
Publication statusPublished - Feb 1 2017

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Sulfur
2,2'-Dipyridyl
Carbon
Reaction intermediates
Electrospray ionization
Atoms
Deprotonation
Temperature
Labeling
Fourier transform infrared spectroscopy
Mass spectrometry
Gases
Thermodynamics
Oxygen
Oxidation
Catalysts
Air

ASJC Scopus subject areas

  • Chemistry(all)
  • Chemical Engineering(all)

Cite this

Hydrolytic cleavage of both CS2 carbon-sulfur bonds by multinuclear Pd(II) complexes at room temperature. / Jiang, Xuan Feng; Huang, Hui; Chai, Yun Feng; Lohr, Tracy Lynn; Yu, Shu Yan; Lai, Wenzhen; Pan, Yuan Jiang; Delferro, Massimiliano; Marks, Tobin J.

In: Nature Chemistry, Vol. 9, No. 2, 01.02.2017, p. 188-193.

Research output: Contribution to journalArticle

Jiang, XF, Huang, H, Chai, YF, Lohr, TL, Yu, SY, Lai, W, Pan, YJ, Delferro, M & Marks, TJ 2017, 'Hydrolytic cleavage of both CS2 carbon-sulfur bonds by multinuclear Pd(II) complexes at room temperature', Nature Chemistry, vol. 9, no. 2, pp. 188-193. 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 ; Marks, Tobin J. / Hydrolytic cleavage of both CS2 carbon-sulfur bonds by multinuclear Pd(II) complexes at room temperature. In: Nature Chemistry. 2017 ; Vol. 9, No. 2. pp. 188-193.
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