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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}
}