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Spontaneous Disproportionation of No2 (N2O4) By Aromatic Hydrocarbons. Formation of Nitrosonium Eda Complexes as Chemical Intermediates

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Strong (orange/red) colourations resulting immediately upon the exposure of nitrogen dioxide and its equilibrium dimer (dinitrogen tetroxide) to various aromatic hydrocarbons (ArH) are shown to arise from the nitrosonium EDA or electron donor-acceptor complexes [ArH, NO+NO3-]. The latter exhibit diagnostic charge-transfer absorptions and characteristic N-O stretching bands in the UV-vis and IR spectra, respectively, that relate directly to ArH/NO+ interactions extant in the EDA complexes previously derived from the authentic nitrosonium salt, NO+PF6-. Time-resolved picosecond spectroscopy establishes the charge-transfer excited state of [ArH, NO+NO3-] to be essentially identical to that from [ArH, NO+BF4-]. Furthermore, the same temporal decay of the spectral transients (ArH+.) from both systems indicates minimal ion-pairing effects of the counterions (NO3- and BF4-) on the kinetics of back electron transfer.

Affiliations: 1: Department of Chemistry, University of Houston, Houston, Texas 77204-5641, U.S.A

10.1163/156856793X00406
/content/journals/10.1163/156856793x00406
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/content/journals/10.1163/156856793x00406
2017-11-20

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