title: Hydrolytic cleavage of both CS2carbon-sulfur bonds by multinuclear Pd(II) complexes at room temperature.
abstract: Developing homogeneous catalysts that convert CS2and 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 CS2carbon-sulfur bonds at 25 °C to produce CO2and trimeric Pd complexes. Oxidation of the trimeric complexes with HNO3regenerates the dimeric starting complexes with the release of SO2and NO2. Isotopic labelling confirms that the carbon and oxygen atoms of CO2originate from CS2and 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 CO2release to yield [(bpy)3Pd3(µ3-S)2](NO3)2(bpy, 2,2'-bipyridine) provides the thermodynamic driving force for the reaction.
authors.affiliation: Beijing Key Laboratory for Green Catalysis and Separation, Laboratory for Self-Assembly Chemistry, Department of Chemistry and Chemical Industry, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China.|College of Materials Science and Opto-electronic Technology and Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing 100049, China.
authors.forename: Xuan-Feng
authors.initials: XF
authors.lastname: Jiang
authors.affiliation: College of Materials Science and Opto-electronic Technology and Key Laboratory of Vacuum Physics, University of Chinese Academy of Sciences, Beijing 100049, China.
authors.forename: Hui
authors.initials: H
authors.lastname: Huang
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
authors.forename: Yun-Feng
authors.initials: YF
authors.lastname: Chai
authors.affiliation: Department of Chemistry and the Center for Surface Science and Catalysis, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Tracy Lynn
authors.initials: TL
authors.lastname: Lohr
authors.affiliation: Beijing Key Laboratory for Green Catalysis and Separation, Laboratory for Self-Assembly Chemistry, Department of Chemistry and Chemical Industry, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124, China.
authors.forename: Shu-Yan
authors.initials: SY
authors.lastname: Yu
authors.affiliation: Department of Chemistry, Renmin University of China, Beijing 100872, China.
authors.forename: Wenzhen
authors.initials: W
authors.lastname: Lai
authors.affiliation: Department of Chemistry, Zhejiang University, Hangzhou 310027, China.
authors.forename: Yuan-Jiang
authors.initials: YJ
authors.lastname: Pan
authors.affiliation: Department of Chemistry and the Center for Surface Science and Catalysis, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Massimiliano
authors.initials: M
authors.lastname: Delferro
authors.affiliation: Department of Chemistry and the Center for Surface Science and Catalysis, Northwestern University, Evanston, Illinois 60208, USA.
authors.forename: Tobin J
authors.initials: TJ
authors.lastname: Marks