Reactive Pathways in the Bromobenzene-Ammonia Dimer Cation Radical: Evidence for a Roaming Halogen Radical
Abstract
Photoinitiated reactions in van der Waals complexes provide a means to examine reactive pathways from well-defined initial geometries. In recent work, we re-examined reactive pathways following resonant two-photon ionization (R2PI) of the chlorobenzene-ammonia (PhCl···NH3) dimer. The dimer cation radical reacts primarily via Cl atom loss, and additional channels corresponding to HCl and H atom loss were identified. The structure of the reactive complex was confirmed as an in-plane σ-type, and computational studies of the dimer cation radical potential energy landscape revealed two nearly isoenergetic arenium ion intermediates (or Wheland intermediates). The intermediate produced from ipso addition was not stable with respect to either Cl or HCl loss, and the relative branching observed in experiment was well reproduced by microcanonical transition state theory (TST) calculations. Here, we report experimental and computational studies of the related PhBr···NH3 dimer, examined for the first time. We present evidence that the dimer structure is also an in-plane σ-type. However, in contrast to the PhCl···NH3 system, calculations predict that the structure of the reactive intermediate corresponds to a distonic ion-radical complex, where the radical density is largely localized on the bromine atom. The calculated barrier to HBr loss is sufficiently high to render this channel nearly insignificant (less than 1% branching) in TST calculations, yet experiment shows a sizable (37%) branching into this channel. We rationalize these results in terms of a roaming Br radical mechanism for HBr formation.
Recommended Citation
S. Nyambo et al., "Reactive Pathways in the Bromobenzene-Ammonia Dimer Cation Radical: Evidence for a Roaming Halogen Radical," Journal of Molecular Structure, vol. 1172, pp. 113 - 118, Elsevier B.V., Nov 2018.
The definitive version is available at https://doi.org/10.1016/j.molstruc.2017.11.122
Department(s)
Chemistry
Research Center/Lab(s)
Center for High Performance Computing Research
Keywords and Phrases
Halobenzenes; Nucleophilic Substitution; Roaming Radical
International Standard Serial Number (ISSN)
0022-2860
Document Type
Article - Journal
Document Version
Citation
File Type
text
Language(s)
English
Rights
© 2018 Elsevier B.V., All rights reserved.
Publication Date
01 Nov 2018
Comments
Support of this research by the National Science Foundation is gratefully acknowledged. This research was also supported in part by National Science Foundation awards OCI-0923037 "MRI: Acquisition of a Parallel Computing Cluster and Storage for the Marquette University Grid (MUGrid)" and CBET-0521602 "Acquisition of a Linux Cluster to Support College-Wide Research & Teaching Activities". R.D. acknowledges support from the U.S. Department of Energy (Grant No. DE-SC0010616 ).