Is the elusive trioxydehydroethene neutral (O2C-CO) detectable in the gas phase?

Citation
S. Peppe et al., Is the elusive trioxydehydroethene neutral (O2C-CO) detectable in the gas phase?, J PHYS CH A, 105(44), 2001, pp. 10139-10145
Citations number
57
Categorie Soggetti
Physical Chemistry/Chemical Physics
Journal title
JOURNAL OF PHYSICAL CHEMISTRY A
ISSN journal
10895639 → ACNP
Volume
105
Issue
44
Year of publication
2001
Pages
10139 - 10145
Database
ISI
SICI code
1089-5639(20011108)105:44<10139:ITETN(>2.0.ZU;2-8
Abstract
The covalently bound radical anion [O2C-CO](-.) is formed when 1,3-dioxolan e-2,5-dione captures an electron followed by retro-cleavage of CH2O. Calcul ations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G(d) level of theory indicate that there are a number of neutral isomers with formula C2O3, ViZ- van der Waals complex O2C - - - CO (rel. energy = 0 kcal mol(-1)), singlet oxiran d ione (+60.9 kcal mol(-1)), triplet OCOCO (+99.4 kcal mol(-1)), covalently b ound triplet O2C-CO (+ 107.6 kcal mol(-1)), singlet trioxapropellane (+171. 9 kcal mol-1) and triplet trioxapropellane (+ 222.4 kcal mol(-1)). Of these , only triplet O2C-CO is accessible by vertical Franck-Condon one-electron oxidation of [O2C-CO](-.). Neutralization reionization experiments of [O2C- CO](-.) (both -NR+ and -NR-) fail to produce recovery signals corresponding to ionized C2O3, which means that if neutral C2O3 is stable, the lifetime must be < 10(-6) sec. The -NR+ spectrum of [O2C-CO](-.) shows peaks corresp onding to CO+. CO2+. and to [O dropC dropC dropO](+.). The last of these sp ecies can only be formed from a decomposing C2O3+. radical cation by a proc ess endothermic by 47 kcal mol(-1) [at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31G (d) level of theory]. Calculations at this same level of theory indicate th at the vertical one-electron oxidation of [O2C-CO](-.) to triplet O2C-CO gr ound state produces the neutral with essentially no excess energy. There ar e two dissociation pathways of this triplet neutral, (i) an endothermic pro cess yielding (CO)-C-3 + (CO2)-C-1 (+ 28.9 kcal mol(-1)), and (ii) an exoth ermic process (-6.8 kcal mol(-1)) with a barrier of 5.4 kcal mol(-1) yieldi ng (CO)-C-1 + (CO2)-C-3. A combination of experimental and theoretical data , suggests that vertical oxidation of [O2C-CO](-.) produces only one neutra l C2O3 isomer; a transient triplet O2C-CO neutral whose lifetime is less th an 10(-6) sec.