Visible-light-induced photochemistry of 2,3-dimethyl-2-butene N[sub 2]O[sub 4] charge-transfer complexes in solid inert matrices at 75 K

Journal Article · Thu Feb 11 04:00:00 EST 1993 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100108a013· OSTI ID:6296436

Blatter, F; Frei, H ^[1]

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1. Lawrence Berkeley Lab., CA (United States)

Continuous-wave laser-induced photochemistry of 2,3-dimethyl-2-butene (DMB)[center dot]s-N[sub 2]O[sub 4] complexes embedded in solid CO[sub 2] and solid Xe at 75 K was observed at wavelengths as long as 488 nm (s: symmetric form (O[sub 2]N-NO[sub 2])). The chemistry was monitored by Fourier transform infrared and UV-visible spectroscopy. Products identified by [sup 15]N and [sup 18]O isotope substitution were 2,3-dimethyl-3-nitroso-2-butyl nitrate (major), 2,3-dimethyl-3-nitro-2-butyl nitrite, and a-N[sub 2]O[sub 3] (both minor). A mechanism is proposed that is distinct from that previously suggested for thermal alkene + N[sub 2]O[sub 4] chemistry in solution and liquid N[sub 2]O[sub 4]. UV-visible spectra of DMB[center dot]s-N[sub 2]O[sub 4], 2-methyl-2-butene[center dot]s-N[sub 2]O[sub 4], and trans-2-butene[center dot]s-N[sub 2]O[sub 4] complexes in solid CO[sub 2] revealed intense new absorptions with maxima at 360, 338, and 296 nm, respectively. These are assigned to charge-transfer transitions. The DMB[center dot]s-N[sub 2]O[sub 4] charge-transfer band extends to 550 nm and is responsible for the observed photochemistry. 23 refs., 5 figs., 1 tab.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6296436
• Journal Information: Journal of Physical Chemistry; (United States), Journal Name: Journal of Physical Chemistry; (United States) Vol. 97:6; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
400500* -- Photochemistry
ALKENES
BUTENES
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
ELECTROMAGNETIC RADIATION
ELEMENTS
EXPERIMENTAL DATA
FLUIDS
GASES
HYDROCARBONS
INFORMATION
LASER RADIATION
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHOTOCHEMICAL REACTIONS
PHOTOCHEMISTRY
RADIATIONS
RARE GASES
SPECTROSCOPY
XENON