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Title: Sorptive Reconstruction of CuMCl4 (M = Al and Ga) Upon Small-Molecule Binding the Competitive Binding of CO and Ethylene

Abstract

Carbonyl adducts to CuMCl{sub 4} (M = Al and Ga) have been characterized by single-crystal and/or powder X-ray diffraction, IR and diffuse reflectance UV/vis spectroscopy. Up to two equivalents of carbon monoxide ({approx}200 cm{sup 3}/g relative to stp) are sorbed at room temperature, with equilibrium binding pressures of below 0.5 atm of CO. The carbonyl bonding is shown to be nonclassical, implicating the dominance of {sigma}-bonding and absence of {pi}-back-bonding. Analysis of the crystalline structures of the parent and adduct phases provides an atomistic picture of the sorptive reconstruction reaction. Comparison of the reactivity of CO and ethylene with these CuMCl{sub 4} materials, as well as other copper(I) halide compounds that exhibit classical and nonclassical modes of bonding, demonstrates the ability to tune the reactivity of the crystalline frameworks with selectivity for carbon monoxide or olefins, respectively.

Authors:
; ;
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL) National Synchrotron Light Source
Sponsoring Org.:
Doe - Office Of Science
OSTI Identifier:
930160
Report Number(s):
BNL-80818-2008-JA
Journal ID: ISSN 0002-7863; JACSAT; TRN: US200822%%1210
DOE Contract Number:
DE-AC02-98CH10886
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of the American Chemical Society; Journal Volume: 128
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COPPER CHLORIDES; ALUMINIUM CHLORIDES; GALLIUM CHLORIDES; SORPTIVE PROPERTIES; CARBON MONOXIDE; ETHYLENE; ADSORPTION; CARBONYLS; ADDUCTS; CRYSTAL STRUCTURE; national synchrotron light source

Citation Formats

Capracotta,M., Sullivan, R., and Martin, J.. Sorptive Reconstruction of CuMCl4 (M = Al and Ga) Upon Small-Molecule Binding the Competitive Binding of CO and Ethylene. United States: N. p., 2006. Web. doi:10.1021/ja063172q.
Capracotta,M., Sullivan, R., & Martin, J.. Sorptive Reconstruction of CuMCl4 (M = Al and Ga) Upon Small-Molecule Binding the Competitive Binding of CO and Ethylene. United States. doi:10.1021/ja063172q.
Capracotta,M., Sullivan, R., and Martin, J.. Sun . "Sorptive Reconstruction of CuMCl4 (M = Al and Ga) Upon Small-Molecule Binding the Competitive Binding of CO and Ethylene". United States. doi:10.1021/ja063172q.
@article{osti_930160,
title = {Sorptive Reconstruction of CuMCl4 (M = Al and Ga) Upon Small-Molecule Binding the Competitive Binding of CO and Ethylene},
author = {Capracotta,M. and Sullivan, R. and Martin, J.},
abstractNote = {Carbonyl adducts to CuMCl{sub 4} (M = Al and Ga) have been characterized by single-crystal and/or powder X-ray diffraction, IR and diffuse reflectance UV/vis spectroscopy. Up to two equivalents of carbon monoxide ({approx}200 cm{sup 3}/g relative to stp) are sorbed at room temperature, with equilibrium binding pressures of below 0.5 atm of CO. The carbonyl bonding is shown to be nonclassical, implicating the dominance of {sigma}-bonding and absence of {pi}-back-bonding. Analysis of the crystalline structures of the parent and adduct phases provides an atomistic picture of the sorptive reconstruction reaction. Comparison of the reactivity of CO and ethylene with these CuMCl{sub 4} materials, as well as other copper(I) halide compounds that exhibit classical and nonclassical modes of bonding, demonstrates the ability to tune the reactivity of the crystalline frameworks with selectivity for carbon monoxide or olefins, respectively.},
doi = {10.1021/ja063172q},
journal = {Journal of the American Chemical Society},
number = ,
volume = 128,
place = {United States},
year = {Sun Jan 01 00:00:00 EST 2006},
month = {Sun Jan 01 00:00:00 EST 2006}
}
  • No abstract prepared.
  • Single crystals of the cubic {tau}-Borides Co{sub 23-x}M{sub x}B{sub 6} (M=Al, Ga, Sn) were synthesised from the elements at temperatures between 1200 and 1500 deg. C. According to the structure refinements one (Ga, Sn: 8c) or two (Al: 4a and 8c) of the four independent metal sites show a mixed occupation Co/M resulting in the compositions Co{sub 20.9}Al{sub 2.1}B{sub 6}, Co{sub 21.9}Ga{sub 1.1}B{sub 6}, and Co{sub 21.4}Sn{sub 1.6}B{sub 6}, respectively. Melts with Indium gave access to Co{sub 23}B{sub 6} as the first binary {tau}-boride (Fm3-barm,a=10.4618(13) A, 104 refl., 14 param., R{sub 1}(F)=0.0132, wR{sub 2}(F{sup 2})=0.0210). With M=Ir mixed occupations occurmore » for all sites and the boron content varies. The composition for the boron-poor single crystal was Co{sub 16.2}Ir{sub 6.8}B{sub 6}. A higher Ir-content enables the uptake of additional boron resulting in a composition Co{sub 12.3}Ir{sub 8.9}B{sub 10.5}. This can be explained be the substitution of metal atoms on the 8c-site by B{sub 4}-tetrahedra. A boron-rich phase was observed for the first time for a {tau}-boride of cobalt. All compositions were confirmed by EDX measurements. - Graphical Abstract: Single crystal investigations on {tau}-borides Co/M/B with M = Al, Ga, In, Sn, V, Ti, Ir explained the substitution processes. Furthermore the yielded the first binary boride, Co{sub 23}B{sub 6}, and a boron-rich Co{sub 12.3}Ir{sub 8.9}B{sub 10.5} containing B{sub 4}-tetrahedra.« less
  • Structural and magnetic properties of Y(Fe{sub 0.8}M{sub 0.2}){sub 11.3}Nb{sub 0.7} compounds with M=Mn, Fe, Co, Ni, Al, and Ga have been investigated. The x-ray diffraction patterns of aligned samples show that, for M=Mn, Fe, Co, Ni, the compounds exhibit easy axis anisotropy while for M=Al and Ga the compounds have planar anisotropy. The anisotropy fields of Y(Fe{sub 0.8}Mn{sub 0.2}){sub 11.3}Nb{sub 0.7} increase monotonously with decreasing temperature. The influence on the Curie temperature and the magnetization due to the various substitutional atoms are discussed. {copyright} {ital 1997 American Institute of Physics.}
  • The effect of impurities at the Cu(1) site in the basal plane of the high-temperature superconductor YBa{sub 2}Cu{sub 3}O{sub 6+2{ital c}} on the oxygen-vacancy phase diagram is investigated by Monte Carlo simulation of an asymmetric next-nearest-neighbor lattice-gas model, in which the impurities are assumed to act as traps for oxygen atoms. First the phase diagram of YBa{sub 2}Cu{sub 3}O{sub 6+2{ital c}} is determined, which shows the high-temperature orthorhombic and tetragonal phases, as well as the low-temperature double-cell orthorhombic and antiorthorhombic phases. Next the high-temperature orthorhombic-to-tetragonal transition of YBa{sub 2}Cu{sub 3{minus}{ital x}}{ital M}{sub {ital x}}O{sub 6+2{ital c}} is studied within amore » single orthorhombic domain. This orthorhombic-to-tetragonal transition is a true phase transition, with a peak in the specific heat, in contrast with the orthorhombic-to-pseudotetragonal transition studied in previous theoretical studies. The orthorhombic-to-tetragonal phase boundary is found to shift to higher oxygen concentrations with increasing impurity concentration. A first-order approximation for the shift of the phase boundary is derived, which agrees with the Monte Carlo results.« less
  • The new compounds Sc{sub 3}Ir{sub 5}B{sub 2} and Sc{sub 2}MIr{sub 5}B{sub 2} with M = Be, Al, Si, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Ga, or Ge were prepared by arc-melting appropriate compressed mixtures of the elemental components in an argon atmosphere. They crystallize tetragonally with Z = 2 in the space group P4/mbm. According to powder diagrams, all compounds are isotypic. Structure determinations based on single-crystal X-ray data were performed for Sc{sub 2}SiIr{sub 5}B{sub 2}, Sc{sub 2}VIr{sub 5}B{sub 2}, and Sc{sub 2}FeIr{sub 5}B{sub 2}. Sc{sub 3}Ir{sub 5}B{sub 2} crystallizes with the Ti{sub 3}Co{sub 5}B{sub 2}-type compounds, whilemore » the quaternary compounds form an ordered substitutional variant of this structure. The M atoms are arranged in rows along [001] with M-M distances of {approximately}300 pm in the rows and {approximately}660 pm between the rows. For the compounds with M = Mn, Fe, or Co, this results in highly anisotropic magnetic properties. Susceptibility measurements with a Faraday balance in the range 7--770 K suggest ferromagnetic coupling in the rows at low temperatures. Between the rows, the coupling was antiferromagnetic for Sc{sub 2}FeIr{sub 5}B{sub 2} (T{sub N} {approx} 190 K) and ferromagnetic for Sc{sub 2}MnIr{sub 5}B{sub 2} (T{sub C} {approx} 115 K, {mu}{sub s} {approx} 1.2 {mu}{sub B}) and for Sc{sub 2}CoIr{sub 5}B{sub 2} (T{sub C} {approx} 135 K, {mu}{sub s} {approx} 1.2 {mu}{sub B}). The temperature dependence of the resistivity was measured for the compounds with M = Si, Mn, Fe, and Co.« less