α,2-, α,3-, and α,4-Dehydrophenol Radical Anions: Formation, Reactivity, and Energetics Leading to the Heats of Formation of α,2-, α,3-, and α,4-Oxocyclohexadienylidene | Zendy

Dana R. Reed | Zendy; Michael Hare | Zendy; Alireza Fattahi | Zendy; Gyusung Chung | Zendy; Mark S. Gordon | Zendy; Steven R. Kass | Zendy

Open Access

α,2-, α,3-, and α,4-Dehydrophenol Radical Anions: Formation, Reactivity, and Energetics Leading to the Heats of Formation of α,2-, α,3-, and α,4-Oxocyclohexadienylidene

Author(s) -

Dana R. Reed,

Michael Hare,

Alireza Fattahi,

Gyusung Chung,

Mark S. Gordon,

Steven R. Kass

Publication year - 2003

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja029571c

Subject(s) - chemistry , reactivity (psychology) , standard enthalpy of formation , hydrogen atom , electron affinity (data page) , thermochemistry , reagent , ion , affinities , radical ion , proton affinity , energetics , ionization energy , medicinal chemistry , ionization , proton , computational chemistry , stereochemistry , molecule , organic chemistry , group (periodic table) , medicine , physics , pathology , quantum mechanics , ecology , biology , alternative medicine , protonation

We have regiospecifically generated the alpha,2-, alpha,3-, and alpha,4-dehydrophenoxide anions by collisional activation of o-, m-, and p-nitrobenzoate. The alpha,2 and alpha,4 isomers also were synthesized by reacting o-benzyne radical anion with carbon dioxide and electron ionization of p-diazophenol. All three dehydrophenol radical anions were differentiated from each other and identified by probing their chemical reactivity with several reagents. Each isomer was converted to phenoxide and its corresponding quinone as well. Thermochemical measurements were carried out on all three radical anions and their hydrogen-atom affinities, proton affinities, and electron binding energies are reported. These measured quantities are combined in thermodynamic cycles to derive the heats of formation of each of the radical anions and their corresponding carbenes (i.e., alpha,2-, alpha,3-, and alpha,4-dehydrophenol). These results are compared to MCQDPT2, G3, G2+(MP2), and B3LYP calculations and experimental data for appropriate reference compounds.

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