Toward Separation and Purification of Olefins Using Dithiolene Complexes: An Electrochemical Approach

Wang, Kun; Stiefel, Edward I.

doi:10.1126/science.291.5501.106

Cited by 230 publications

(248 citation statements)

References 23 publications

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“…Apparently, there is a significant need to develop novel alternative C 2 H 2 /C 2 H 4 separation approaches. Some recent attempts, hydrogenation by non-precious metal alloy catalysts 44 , ionic liquid extraction 45 , and π-complexation 46 , have been made to reduce the cost or to enhance the selectivities. The realization of our first example of microporous MOF materials for such challenging separation highlights the very promise of the emerging microporous MOFs to resolve this very important industrial separation task in the future.…”

Section: Discussionmentioning

confidence: 99%

Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

et al. 2011

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separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C 2 H 2 /C 2 H 4 have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-

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Section: Discussionmentioning

confidence: 99%

Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

et al. 2011

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“…In particular, the ground-state formulation has a bearing on the reactivity of such complexes, since Stiefel and coworkers have found that similar compounds can selectively and reversibly bind olefins [16] with potentially large impact on industrial olefin separation processes. Clearly, the question whether ligand radicals persist in such complexes or not is at the heart of the formulation of a correct reaction mechanism.…”

Section: Ma C H T U N G T R E N N U N G (L Bumentioning

confidence: 99%

Description of the Ground‐State Covalencies of the Bis(dithiolato) Transition‐Metal Complexes from X‐ray Absorption Spectroscopy and Time‐Dependent Density‐Functional Calculations

Ray

DeBeer

Solomon

et al. 2007

Chemistry A European J

217

227

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The electronic structures of [M(L(Bu))(2)](-) (L(Bu)=3,5-di-tert-butyl-1,2-benzenedithiol; M=Ni, Pd, Pt, Cu, Co, Au) complexes and their electrochemically generated oxidized and reduced forms have been investigated by using sulfur K-edge as well as metal K- and L-edge X-ray absorption spectroscopy. The electronic structure content of the sulfur K-edge spectra was determined through detailed comparison of experimental and theoretically calculated spectra. The calculations were based on a new simplified scheme based on quasi-relativistic time-dependent density functional theory (TD-DFT) and proved to be successful in the interpretation of the experimental data. It is shown that dithiolene ligands act as noninnocent ligands that are readily oxidized to the dithiosemiquinonate(-) forms. The extent of electron transfer strongly depends on the effective nuclear charge of the central metal, which in turn is influenced by its formal oxidation state, its position in the periodic table, and scalar relativistic effects for the heavier metals. Thus, the complexes [M(L(Bu))(2)](-) (M=Ni, Pd, Pt) and [Au(L(Bu))(2)] are best described as delocalized class III mixed-valence ligand radicals bound to low-spin d(8) central metal ions while [M(L(Bu))(2)](-) (M=Cu, Au) and [M(L(Bu))(2)](2-) (M=Ni, Pd, Pt) contain completely reduced dithiolato(2-) ligands. The case of [Co(L(Bu))(2)](-) remains ambiguous. On the methodological side, the calculation led to the new result that the transition dipole moment integral is noticeably different for S(1s)-->valence-pi versus S(1s)-->valence-sigma transitions, which is explained on the basis of the differences in radial distortion that accompany chemical bond formation. This is of importance in determining experimental covalencies for complexes with highly covalent metal-sulfur bonds from ligand K-edge absorption spectroscopy.

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“…They have attracted the interest of scientists due to their special structural features and physical properties, which include novel catalytic, non-linear optical, conductive, fluorescent and magnetic properties [1][2][3][4][5][6][7]. Among these compounds, the transition metal complexes anion (based on the thiocyanate or isothiocyanate ligand) attracts much interest as these ions may coordinate either through the N or S atom as a monodentate ligand, or though N and S atoms as a bridging ligand, forming some complexes with one-, two-or three-dimensional networks [4,[8][9][10].…”

Section: Introductionmentioning

confidence: 99%

Two Organic Cation Salts Containing Tetra(isothiocyanate)cobaltate(II): Synthesis, Crystal Structures, Spectroscopic, Optical and Magnetic Properties

Zhang

Yan

et al. 2017

Crystals

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Abstract:Single crystals of two hybrid organic-inorganic molecular solids, benzyl pyridinium tetra(isothiocyanate)cobalt ([BzPy] 2 [Co(NCS) 4 ]) (1) and benzyl quinolinium tetra(isothiocyanate)cobalt ([BzQl] 2 [Co(NCS) 4 ]) (2), were grown using a slow evaporation growth technique at room temperature and their IR, UV-Vis, X-ray crystal structures, luminescence, and magnetism were reported. The crystal structural analysis revealed that two molecular solids crystallize in the monoclinic space group P2 1 /c of 1 and P2 1 /n of 2. The cations form a dimer through weak C-H···π/π···π interactions in 1 and 2, and the adjacent cation (containing N(6) atom) in 2 forms a columnar structure through π···π weak interactions between the quinoline and benzene rings, while the anions in 1 form a layer structure via short S···Co interactions. The anions (A) and cations (C) are arranged alternatively into a column in the sequence of ···A-CC-A-CC-A··· for 1, while the two anions and cationic dimer in 2 form an alliance by the C-H···π, C-H···S and C-H···N hydrogen bonds. A weak S···π interaction was found in 1 and 2. The two molecular solids show a broad fluorescence emission around 400 nm in the solid state at room temperature, and weak antiferromagnetic coupling behavior when the temperature is lowered.

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Toward Separation and Purification of Olefins Using Dithiolene Complexes: An Electrochemical Approach

Cited by 230 publications

References 23 publications

Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

Rationally tuned micropores within enantiopure metal-organic frameworks for highly selective separation of acetylene and ethylene

Description of the Ground‐State Covalencies of the Bis(dithiolato) Transition‐Metal Complexes from X‐ray Absorption Spectroscopy and Time‐Dependent Density‐Functional Calculations

Two Organic Cation Salts Containing Tetra(isothiocyanate)cobaltate(II): Synthesis, Crystal Structures, Spectroscopic, Optical and Magnetic Properties

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