Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene

Lawrence M. Goldman; David R. Glowacki; Barry K. Carpenter

doi:10.1021/ja1095717

Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene

Lawrence M. Goldman, David R. Glowacki, Barry K. Carpenter

Research output: Contribution to journal › Article (Academic Journal) › peer-review

38 Citations (Scopus)

Abstract

A molecular dynamics simulation reveals the occurrence of nonstatistical dynamical effects in the ring-opening and subsequent [1,5] H migration of bicyclo[2.1.0]pent-2-ene. The symptoms of the effects do not show up in the overall kinetics or product branching ratios of the reaction, which are well explained by a master-equation analysis, but in an oscillatory preference for migration of the two methylene hydrogens. It is predicted that these oscillations could have an observable effect on final product ratios in isotopically labeled analogues, and that the effect might be greater in certain solvents than in the gas phase.

Original language	English
Pages (from-to)	5312-5318
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	133
Issue number	14
DOIs	https://doi.org/10.1021/ja1095717
Publication status	Published - 13 Apr 2011

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title = "Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene",

abstract = "A molecular dynamics simulation reveals the occurrence of nonstatistical dynamical effects in the ring-opening and subsequent [1,5] H migration of bicyclo[2.1.0]pent-2-ene. The symptoms of the effects do not show up in the overall kinetics or product branching ratios of the reaction, which are well explained by a master-equation analysis, but in an oscillatory preference for migration of the two methylene hydrogens. It is predicted that these oscillations could have an observable effect on final product ratios in isotopically labeled analogues, and that the effect might be greater in certain solvents than in the gas phase.",

author = "Goldman, {Lawrence M.} and Glowacki, {David R.} and Carpenter, {Barry K.}",

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T1 - Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene

AU - Goldman, Lawrence M.

AU - Glowacki, David R.

AU - Carpenter, Barry K.

PY - 2011/4/13

Y1 - 2011/4/13

N2 - A molecular dynamics simulation reveals the occurrence of nonstatistical dynamical effects in the ring-opening and subsequent [1,5] H migration of bicyclo[2.1.0]pent-2-ene. The symptoms of the effects do not show up in the overall kinetics or product branching ratios of the reaction, which are well explained by a master-equation analysis, but in an oscillatory preference for migration of the two methylene hydrogens. It is predicted that these oscillations could have an observable effect on final product ratios in isotopically labeled analogues, and that the effect might be greater in certain solvents than in the gas phase.

AB - A molecular dynamics simulation reveals the occurrence of nonstatistical dynamical effects in the ring-opening and subsequent [1,5] H migration of bicyclo[2.1.0]pent-2-ene. The symptoms of the effects do not show up in the overall kinetics or product branching ratios of the reaction, which are well explained by a master-equation analysis, but in an oscillatory preference for migration of the two methylene hydrogens. It is predicted that these oscillations could have an observable effect on final product ratios in isotopically labeled analogues, and that the effect might be greater in certain solvents than in the gas phase.

U2 - 10.1021/ja1095717

DO - 10.1021/ja1095717

M3 - Article (Academic Journal)

C2 - 21417477

VL - 133

SP - 5312

EP - 5318

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 14

ER -

Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene

Abstract

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