The reaction between aluminium and dimethyl ether Comparative study of density functional theory and EPR results

Fängström, Torbjörn; Kirrander, Adam; Eriksson, Leif A.; Lunell, Sten

doi:10.1039/a706667h

Cited by 11 publications

(15 citation statements)

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“…For reactions between Al/Al ϩ and O͑CH 3 ) 2 , Parnis et al 11 obtained the binding energy of Al-O͑CH 3 ) 2 through temperature dependence measurements of reaction equilibrium constants, and Bouchard et al 12 measured the binding energy of Al ϩ -O͑CH 3 ) 2 using laserablation high-pressure mass spectrometry. The formation of the Al association complex as well as insertion products was revealed by Chenier et al electron paramagnetic resonance 13 ͑EPR͒ and Kasai electron spin resonance 14 ͑ESR͒ measurements and Sakai 15 and Fänström et al 16 theoretical predictions. For transition metals, Burnier et al 17 showed the formation of Fe ϩ -(CH 2 O) by ion cyclotron resonance mass spectrometric measurements of the Fe ϩ reaction with dimethyl ether, whereas Pedersen et al 18 identified the association complex of Zr-O͑CH 3 ) 2 in a combined spectroscopic, kinetic, and theoretical study.…”

Section: Introductionmentioning

confidence: 91%

Zero-electron-kinetic-energy photoelectron spectroscopy of transition-metal—ether complexes: Y-O(CH3)2, Y-O(CD3)2, Y-[O(CH3)2]2, and Y-[O(CD3)2]2

Rothschopf

Yang

2002

The Journal of Chemical Physics

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The yttrium complexes with one and two dimethyl ethers and their deuterated derivatives are prepared with laser vaporization molecular beam techniques, identified with photoionization time-of-flight mass spectrometry, and investigated with pulsed-field-ionization zero-electronkinetic-energy ͑ZEKE͒ photoelectron spectroscopy and ab initio calculations. Adiabatic ionization potentials and yttrium-oxygen stretch and ether-based vibrations are measured for the 1:1 and 1:2 complexes. Fermi interactions are observed from the ZEKE spectra of the 1:1 species. The ground electronic states of the monoligand complexes are determined to be 2 A 2 for the neutral and 1 A 1 for the singly charged positive ion, both in C 2v symmetry, with yttrium binding to oxygen. The coordination of a second ether forms a diligand complex with a linear oxygen-yttrium-oxygen configuration. This is the first electronic-vibrational spectroscopic study of yttrium-polyatomic molecule complexes and weakly bound metal complexes with two or more polyatomic molecules.

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Section: Introductionmentioning

confidence: 91%

Zero-electron-kinetic-energy photoelectron spectroscopy of transition-metal—ether complexes: Y-O(CH3)2, Y-O(CD3)2, Y-[O(CH3)2]2, and Y-[O(CD3)2]2

Rothschopf

Yang

2002

The Journal of Chemical Physics

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“…Reactions of magnesium, titanium, and actinide cations with DME have been studied in the gas phase, in which the M(OCH 3 ) + cations as well as higher aggregations were found to be the major reaction products. − Formation of the CH 3 OMCH 3 + intermediates followed by β-hydrogen transfer and methane elimination was also proposed as a reaction channel for titanium and iron, − which were further supported by density functional calculations. , While most gas phase studies have focused on metal cation reactions with DME, experimental information regarding neutral metal reactions has been derived mainly from studies in cryogenic matrices. In the early electron spin resonance and infrared investigations on the reactions of aluminum and silicon with DME, the M(DME) complexes and C–O bond insertion products were characterized, − and they also agreed with theoretical interpretations. − Our recent infrared work on the reactions of thorium and uranium atoms and DME revealed that the Th(CH 3 OCH 3 ) and U(CH 3 OCH 3 ) complexes were produced first during sample annealing, which isomerized to the divalent insertion products under visible irradiation . Further UV irradiation produced the M(IV) (CH 3 ) 2 MO molecules with MO double bonds as well as the (CH 3 O) 2 M(CH 3 ) 2 molecules.…”

Section: Introductionmentioning

confidence: 64%

Matrix Infrared Spectroscopic and Theoretical Studies on the Reactions of Scandium, Yttrium, and Lanthanide Metal Atoms with Dimethyl Ether

Gong

Andrews

2011

J. Phys. Chem. A

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Reactions of laser-ablated scandium, yttrium, lanthanum, and several lanthanide metal atoms with dimethyl ether have been studied using matrix isolation infrared spectroscopy. Identifications of the major products, M(CH(3)OCH(3)) and CH(3)OMCH(3) (M = Sc, Y, La, Ce, Gd, Tb, Yb, and Lu), are supported by experiments with deuterium substitution as well as theoretical calculations. It is found that most ground-state metal atoms react with dimethyl ether to give the M(CH(3)OCH(3)) complexes spontaneously on annealing, which isomerize to the CH(3)OMCH(3) insertion products with visible irradiation. Density functional calculations reveal that the M(CH(3)OCH(3)) complexes possess C(2v) symmetry with metal atoms bound to the oxygen side of dimethyl ether, and bent geometries are found for the inserted CH(3)OMCH(3) molecules with direct M-O and C-O bonds. All of these products have the same ground states as their corresponding metal atoms except for Tb. Although the Lu(CH(3)OCH(3)) complex is predicted to be a stable molecule, it is not observed in the experiment due to the low energy barrier for the subsequent C-O bond insertion reaction.

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“…These are within the range of deviations reported in similar theoretical studies. 7,10 It is interesting to note that the calculated zero-point energy of the C Me −O insertion product is lower than that of the C Et −O insertion product by ≈7 kcal/mol, while the energy difference between the cis and trans conformers is <2 kcal/mol. Al Atom C−C Insertion Products of MEE and DEE.…”

Section: Mhzmentioning

confidence: 99%

Activation of C–O and C–C Bonds and Formation of Novel HAlOH-Ether Complexes: An EPR Study of the Reaction of Ground-State Al Atoms with Methylethyl Ether and Diethyl Ether

2012

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Reaction mixtures, containing Al atoms and methylethyl ether (MEE) or diethyl ether (DEE) in an adamantane matrix, were prepared with the aid of a metal-atom reactor known as a rotating cryostat. The EPR spectra of the resulting products were recorded from 77-260 K, at 10 K intervals. Al atoms were found to insert into methyl-O, ethyl-O, and C-C bonds to form CH(3)AlOCH(2)CH(3), CH(3)OAlCH(2)CH(3), and CH(3)OCH(2)AlCH(3), respectively, in the case of MEE while DEE produced CH(3)CH(2)AlOCH(2)CH(3) and CH(3)AlCH(2)OCH(2)CH(3), respectively. From the intensity of the transition lines attributed to the Al atom C-O insertion products of MEE, insertion into the methyl-O bond is preferred. The Al hyperfine interaction (hfi) extracted from the EPR spectra of the C-O insertion products was greater than that of the C-C insertion products, that is, 5.4% greater for the DEE system and 7% greater for the MEE system. The increase in Al hfi is thought to arise from the increased electron-withdrawing ability of the substituents bonded to Al. Besides HAlOH, resulting from the reaction of Al atoms with adventitious water, novel mixed HAlOH:MEE and HAlOH:DEE complexes were identified with the aid of isotopic studies involving H(2)(17)O and D(2)O. The Al and H hfi of HAlOH were found to decrease upon complex formation. These findings are consistent with the nuclear hfi calculated using a density functional theory (DFT) method with close agreement between theory and experiment occurring at the B3LYP level using a 6-311+G(2df,p) basis set.

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The reaction between aluminium and dimethyl ether Comparative study of density functional theory and EPR results

Cited by 11 publications

References 0 publications

Zero-electron-kinetic-energy photoelectron spectroscopy of transition-metal—ether complexes: Y-O(CH3)2, Y-O(CD3)2, Y-[O(CH3)2]2, and Y-[O(CD3)2]2

Zero-electron-kinetic-energy photoelectron spectroscopy of transition-metal—ether complexes: Y-O(CH3)2, Y-O(CD3)2, Y-[O(CH3)2]2, and Y-[O(CD3)2]2

Matrix Infrared Spectroscopic and Theoretical Studies on the Reactions of Scandium, Yttrium, and Lanthanide Metal Atoms with Dimethyl Ether

Activation of C–O and C–C Bonds and Formation of Novel HAlOH-Ether Complexes: An EPR Study of the Reaction of Ground-State Al Atoms with Methylethyl Ether and Diethyl Ether

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