Preparation, Structural Characterization, and Thermochemistry of an Isolable 4-Arylphenoxyl Radical | Zendy

Thomas R. Porter | Zendy; Werner Kaminsky | Zendy; James M. Mayer | Zendy

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Preparation, Structural Characterization, and Thermochemistry of an Isolable 4-Arylphenoxyl Radical

Author(s) -

Thomas R. Porter,

Werner Kaminsky,

James M. Mayer

Publication year - 2014

Publication title -

the journal of organic chemistry

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 1.2

H-Index - 228

eISSN - 1520-6904

pISSN - 0022-3263

DOI - 10.1021/jo501531a

Subject(s) - chemistry , radical , bond dissociation energy , thermochemistry , electron paramagnetic resonance , toluene , delocalized electron , homolysis , photochemistry , reagent , hydrogen atom , radical ion , dissociation (chemistry) , organic chemistry , alkyl , ion , physics , nuclear magnetic resonance

The preparation and full characterization of the 4-(nitrophenyl)phenoxyl radical, 2,6-di-(t)butyl-4-(4'-nitrophenyl) phenoxyl radical ((t)Bu2NPArO(•)) is described. This is a rare example of an isolable and crystallographically characterized phenoxyl radical and is the only example in which the parent phenol is also crystallographically well-defined. Analysis of EPR spectra indicates some spin delocalization onto the secondary aromatic ring and nitro group. Equilibrium studies show that the corresponding phenol has an O-H bond dissociation free energy (BDFE) of 77.8 ± 0.5 kcal mol(-1) in MeCN (77.5 ± 0.5 kcal mol(-1) in toluene). This value is higher than related isolated phenoxyl radicals, making this a useful reagent for hydrogen atom transfer (HAT) studies. Additional thermochemical and spectroscopic parameters are also discussed.

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