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Title: Unimolecular thermal fragmentation of ortho-benzene.

Abstract

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments o-C{sub 6}H{sub 4}{sup +} {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4}{sup +}{Delta}{yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimental {Delta}{sub rxn}H{sub 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connectedmore » quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH-HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
939552
Report Number(s):
ANL/CHM/JA-57209
Journal ID: ISSN 0021-9606; JCPSA6; TRN: US200823%%151
DOE Contract Number:
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Chem. Phys.; Journal Volume: 126; Journal Issue: 4 ; 2007
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AROMATICS; BENZYL RADICALS; DISSOCIATION; ELECTRONIC STRUCTURE; FRAGMENTATION; PHENYL RADICALS; PYROLYSIS; CHEMICAL REACTION KINETICS

Citation Formats

Zhang, X., Maccarone, A. T., Nimlos, M. R., Kato, S., Bierbaum, V. M., Ellison, G. B., Ruscic, B., Simmonett, A. C., Allen, W. D., Schaefer, H. F., Chemistry, Univ. of Colorado, NREL, and Univ. of Georgia. Unimolecular thermal fragmentation of ortho-benzene.. United States: N. p., 2007. Web. doi:10.1063/1.2409927.
Zhang, X., Maccarone, A. T., Nimlos, M. R., Kato, S., Bierbaum, V. M., Ellison, G. B., Ruscic, B., Simmonett, A. C., Allen, W. D., Schaefer, H. F., Chemistry, Univ. of Colorado, NREL, & Univ. of Georgia. Unimolecular thermal fragmentation of ortho-benzene.. United States. doi:10.1063/1.2409927.
Zhang, X., Maccarone, A. T., Nimlos, M. R., Kato, S., Bierbaum, V. M., Ellison, G. B., Ruscic, B., Simmonett, A. C., Allen, W. D., Schaefer, H. F., Chemistry, Univ. of Colorado, NREL, and Univ. of Georgia. Mon . "Unimolecular thermal fragmentation of ortho-benzene.". United States. doi:10.1063/1.2409927.
@article{osti_939552,
title = {Unimolecular thermal fragmentation of ortho-benzene.},
author = {Zhang, X. and Maccarone, A. T. and Nimlos, M. R. and Kato, S. and Bierbaum, V. M. and Ellison, G. B. and Ruscic, B. and Simmonett, A. C. and Allen, W. D. and Schaefer, H. F. and Chemistry and Univ. of Colorado and NREL and Univ. of Georgia},
abstractNote = {The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments o-C{sub 6}H{sub 4}{sup +} {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4}{sup +}{Delta}{yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimental {Delta}{sub rxn}H{sub 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH-HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.},
doi = {10.1063/1.2409927},
journal = {J. Chem. Phys.},
number = 4 ; 2007,
volume = 126,
place = {United States},
year = {Mon Jan 01 00:00:00 EST 2007},
month = {Mon Jan 01 00:00:00 EST 2007}
}
  • The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C{sub 6}H{sub 4} + {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4} + {Delta} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimentalmore » {Delta}{sub rxn}H{sub 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less
  • Infrared multiple photon (IRMP) photochemical activation of gas-phase ions trapped in an ion cyclotron resonance (ICR) spectrometer has been used to study the mechanism of a gas-phase negative ion unimolecular decomposition. Upon irradiation with a CO/sub 2/ laser (both high-power pulsed and low-power continuous wave (CW)), tert-butoxide anion, trapped in a pulsed ICR spectrometer, decomposes to yield acetone enolate anion and methane. The mechanism of this formal 1,2-elimination reaction was probed by measuring competitive hydrogen isotope effects (both primary and secondary) in the IR laser photolysis of 2-methyl-2-propoxide-1,1,1-d/sub 3/ (1) and 2-methyl-2-propoxide-1,1,1,3,3,3-d/sub 6/ (2) anions. Unusually large secondary isotope effectsmore » (pulsed laser, 1.9 for 1 and 1.7 for 2; cw laser, 8 for (1) and small primary isotope effects (pulsed laser, 1.6 for 1 and 2; cw laser, 2.0 for (1) were observed. These isotope effects, particularly the large difference in energy dependence of the primary and secondary effects, are consistent only with a stepwise mechanism involving initial bond cleavage to an intermediate ion-molecular complex followed by a hydrogen transfer within the intermediate complex. The observed secondary isotope effect have been modelled by using statistical reaction rate (RRKM) theory. The implications of this study for several previously reported unimolecular ion decompositions are also discussed.« less
  • The kinetic energy release distributions in the fragmentation C/sub 4/H/sub 6//sup +/..-->..C/sub 3/H/sub 3//sup +/+CH/sub 3/ at selected energies are reported and are compared with the analogous distributions from ''metastable'' C/sub 4/H/sub 6//sup +/ and from C/sub 2/H/sub 2//sup +/+C/sub 2/H/sub 4/ collision complexes. The data seem to reflect the role of angular momentum in the collision experiments, as predicted by the Langevin model of the quasiequilibrium theory.
  • High precision measurements of the vapor pressure differences between some deuterated benzenes B-d/sub x/ (x=1, para-2, and 6) and protio benzene B-d/sub 0/; between para- and ortho-, and para- and meta-dideuterobenzene; and between perdeuterocyclohexane C-d/sub 12/ and protiocyclohexane C-d/sub 0/ were made from near the freezing point to the normal boiling point. The data are best represented as the logarithmic ratios ln R (d/sub 6/) =ln (P/sub d/0/P/sub d/6) =1226.5/T/sup 2/-12.178/T, ln R (para/ortho) =ln (P/sub parahyphend/2/P/sub orthohyphend/2) =2.6/T/sup 2/, and ln R (para/meta) =ln (P/sub parahyphend/2/P/sub metahyphend/2) =-2.0/T/sup 2/, together with the deviations from the law of the meanmore » ..delta.. (d1) =6-(ln R (d/sub 6/)/lnR (d/sub 1/))=0.177-3.6 x 10/sup -4/t and ..delta.. (d/sub 2hyphenpara/=3-(ln R (d/sub 6/)/ln R (d/sub 2hyphenpara/))=0.028 +1.0 x 10/sup -4/t. The isotope effects are inverse and display significant deviations from the law of the mean. The cyclohexane results are given by ln R (C-d/sub 12/) =-2188.4/T/sup 2/-18.587/T. New measurements of the vapor pressures of benzene--cyclohexane solutions are also reported between 5 and 80 /sup 0/C. The data are in good agreement with the best earlier work. Excess free energies of the equimolar solutions B-h/sub 6//B-d/sub 6/ and C-h/sub 12//C-d/sub 12/ have been measured between 20 and 80 /sup 0/C. Suitable fits to the data yield the following results (30 /sup 0/C); G/sup ex/(B-h/B-d), G/sup ex/(C-h/C-d); H/sup ex/(B-h/B-d),« less