Absorption of Ethylene by Solid Cuprous Chloride

Tropsch, Hans; Mattox, W. J.

doi:10.1021/ja01309a044

Cited by 27 publications

(10 citation statements)

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“…[3,[92][93][94] These compounds have limited stability and decompose unless low temperatures and high ethylene pressures are maintained. This reversible adduct formation by Cu I has been exploited in the separation of olefins like ethylene from paraffins and in important catalytic processes such as the oxychlorination of ethylene.…”

Section: Structurally Characterized Copper(i)-ethylene Complexesmentioning

confidence: 99%

Structurally Characterized Coinage‐Metal–Ethylene Complexes

Dias

2008

Eur J Inorg Chem

127

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Despite the interest in them, easily isolable and thermally stable CuI, AgI, and AuI complexes of ethylene are stilllimited and get increasingly sparse as one descends the group 11 triad towards gold. Recently, there have been some notable developments in this field, including the isolation of gold–ethylene complexes and coinage‐metal adducts with more than one ethylene molecule on a metal center. This article focuses on the chemistry of coinage‐metal–ethylene adducts that have been synthesized and characterized by X‐ray crystallography. Thus far, bidentate and tridentate donors based on nitrogen appear to be the ligands of choice forstabilizing species with an M–C2H4 (M = CuI, AgI, and AuI) moiety. Weakly donating ligands and anions are also commonly used, as they do not interfere with and displace the ethylene from the metal center. The ethylene 13C NMR chemical shift provides useful information about the nature of the metal–ethylene interaction. In some adducts (especially those with relatively weak M–C2H4 interactions), the change in the C=C bond length upon coordination to the metal site is difficult to discern because it falls within the errors associated with the crystallographically determined C=C bond length value. IR and Raman C=C stretching data would be useful but, probably due to the very weak nature of the IR band and the lack of convenient access to the Raman instruments, are often not reported. In this microreview, results from some computational and gas‐phase spectroscopic studies are also provided for comparison.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)

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Section: Structurally Characterized Copper(i)-ethylene Complexesmentioning

confidence: 99%

Structurally Characterized Coinage‐Metal–Ethylene Complexes

Dias

2008

Eur J Inorg Chem

127

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“…It has been known for many years that copper(I) salts such as cuprous chloride react with ethylene to form adducts, but these compounds have limited stability and decompose unless low temperatures and high ethylene pressures are maintained. ,, Thompson and co-workers first reported structural data on the copper ethylene complex [HB(3,5-(CH 3 ) 2 Pz) 3 ]Cu(C 2 H 4 ) in 1983 . However, this adduct also loses ethylene easily under reduced pressure.…”

Section: Introductionmentioning

confidence: 99%

Copper(I) Ethylene Complexes Supported by 1,3,5-Triazapentadienyl Ligands with Electron-Withdrawing Groups

et al. 2012

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The fluorinated 1,3,5-triazapentadienyl ligands [N{(C 3 F 7 )C(2-(NO 2 )-C 6 H 4 )N} 2 ] − , [N{(C 3 F 7 )C(4-(NO 2 )C 6 H 4 )N} 2 ] − , [N{(C 3 F 7 )C(2-(CF 3 )C 6 H 4 )N} 2 ] − , and [N{(C 3 F 7 )C(2-F,6-(CF 3 )C 6 H 3 )N} 2 ] − have been used as supporting ligands in copper(I) ethylene chemistry. [N{and [N{(C 3 F 7 )C(2-F,6-(CF 3 )C 6 H 3 )N} 2 ]Cu(C 2 H 4 ) (10) are easily isolable, thermally stable solids and display their ethylene proton and carbon resonances in the δ 3.68−3.48 and 85.2−87.6 ppm regions, respectively. X-ray crystal structures reveal that 7−10 feature trigonal-planar copper sites and κ 2 -bonded, U-shaped triazapentadienyl ligands. The Cu(I) carbonyl adducts [N{(C 3 F 7 )C(2-(NO 2 )C 6 H 4 )N} 2 ]Cu(CO)(NCCH 3 ) (16) and [N{(C 3 F 7 )C(4-(NO 2 )C 6 H 4 )N} 2 ]Cu(CO)(NCCH 3 ) (17) have also been synthesized, and they have pseudotetrahedral copper sites. The CO stretching frequencies of the compounds 16 and 17 and ethylene 13 C NMR chemical shift data of 7−10 suggest that these molecules have rather acidic copper sites and weakly donating triazapentadienyl ligands. Article pubs.acs.org/Organometallics

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“…The concept of using these complexes as adsorbents derives from early discoveries by chemists that lower olefins can form liquid or solid complexes with Cu + or Ag + salts with an ∼1:1 ratio. [4][5][6][7][8] These complexes can release olefins upon mild heating, indicating that the complexation is not very strong. There are numerous studies addressing the dispersion of Cu + or Ag + salts on various supports, [9][10][11][12][13][14][15][16][17] such as silica, alumina, zeolites, and clays, or grafting the metal atoms in polymer membrane.…”

Section: Introductionmentioning

confidence: 99%

Olefin Adsorption on Silica-Supported Silver Salts − A DFT Study

2006

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Recent experiments have shown that silver salts supported on mesoporous silicas display excellent adsorption selectivities of ethylene over ethane and propylene over propane. Employing the techniques of density functional theory, we have investigated the fundamental bases of this separation process by examining silver salts dispersed on model silica surfaces. Our model system includes Ag+ cations, their counteranions, silica supports, and surface silanols. Both adsorption geometries and energetics of ethylene and propylene were explored. Our results indicate that the nature of the Ag-olefin interaction is predominantly hybridization between Ag d and olefin pi states, which is supported by analyses of electron density difference plots and density of states. The counteranions, such as NO3- were found to interact strongly with surface silanols through multiple hydrogen bonds but have limited effect on the adsorption energy of olefins on the Ag+ cations. The current work supports recent experiments, which indicate that Ag-salt/silica may be a very promising adsorbent for olefin/paraffin separation.

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Absorption of Ethylene by Solid Cuprous Chloride

Abstract: Only a few instances of the absorption of ethylene by cuprous chloride have been recorded in the literature. These absorptions were observed at atmospheric pressure and, usually, with aqueous solutions.

Cited by 27 publications

References 0 publications

Structurally Characterized Coinage‐Metal–Ethylene Complexes

Structurally Characterized Coinage‐Metal–Ethylene Complexes

Copper(I) Ethylene Complexes Supported by 1,3,5-Triazapentadienyl Ligands with Electron-Withdrawing Groups

Olefin Adsorption on Silica-Supported Silver Salts − A DFT Study

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