NDLI: Nucleophilic Aromatic Substitution with Dianions: Reactions Driven by the Release of Coulomb Repulsion

Content Provider	Springer Nature Link
Author	Eanes, Allison D. Noin, Diogo O. Kebede, Maheteme K. Gronert, Scott
Copyright Year	2013
Abstract	The reactions of a nucleophilic dianion with a series of activated aryl bromides were studied in the gas phase. Nucleophilic aromatic substitution (S$_{N}$Ar) as well as proton transfer reactions were observed. Rate constants and branching ratios were determined for all the reactions and the experimental data are supported by ab initio calculations. Reactions with bis-trifluoromethylbromobenzenes give only S$_{N}$Ar reactions and the rate constants follow the expected pattern, with substituents at the ortho and para positions having the greatest impact. Reactions of polyfluorobromobenzenes give a mix of proton transfer (when possible) and S$_{N}$Ar, with both bromide and fluoride acting as leaving groups. The latter is much less thermodynamically favorable but is the dominant pathway in each case. The selectivity of the reactions indicate that the products are determined early on the potential energy surface, before there is significant cleavage of the bond to the leaving group—the reaction is potentially directed by the initial formation of a hydrogen bond with the arene. The computational data also suggest that hydrogen bonding in the product ion–ion complexes can stabilize the system until there is sufficient charge separation to use the internal Coulomb repulsion to drive the reactions to products. Overall, the results highlight (1) the ability of multiply-charged systems to efficiently funnel their Coulomb repulsion into reaction processes that are intrinsically unfavorable, and (2) the high degree of selectivity that can be attained even in systems with multiple, low-barrier pathways. Figure ᅟ
Starting Page	10
Ending Page	17
Page Count	8
File Format	PDF
ISSN	10440305
Journal	Journal of The American Society for Mass Spectrometry
Volume Number	25
Issue Number	1
e-ISSN	18791123
Language	English
Publisher	Springer US
Publisher Date	2013-10-18
Publisher Institution	The American Society for Mass Spectrometry
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Ion-ion Dianion Gas-phase reaction Nucleophilic aromatic substitution Analytical Chemistry Biotechnology Organic Chemistry Proteomics Bioinformatics
Content Type	Text
Resource Type	Article
Subject	Spectroscopy Structural Biology

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