Structures, thermochemical properties (enthalpy, entropy and heat capacity), rotation barriers, and peroxide bond energies of vinyl, allyl, ethynyl and phenyl hydroperoxidesElectronic supplementary information (ESI) available. Structures, geometry parameters, thermochemical properties, rotation barriers and peroxide bond energies of vinyl, allyl, ethynyl and phenyl hydroperoxides. See http://www.rsc.org/suppdata/cp/b1/b111303h/Presented at the Bunsen Discussion on Formation and Degradation of Hydrocarbons

Alkenyl and Aryl Peroxides

“…It was also found that the calculated O−O bond lengths in alkenyl peroxides are only slightly longer than in alkyl peroxides, whereas the C−O bond lengths are considerably shorter . Calculations of alkynyl peroxides resulted in especially long O−O and especially short C−O bonds.…”

“…As indicatedi nS cheme 1, this can be rationalized by the fact that homolytic cleavage generates the reso- [a] Dr.M.K lussmann Max-Planck-Institut fürK ohlenforschung Kaiser-Wilhelm-Platz 1, 45470 Mülheim an der Ruhr (Germany) E-mail:klusi@mpi-muelheim.mpg.de nance stabilized radicals 4, 6,a nd 7,r espectively,w ith partial carbonyl character,b esideso xyl radicals 5.O rbital interactions of the p-system with the oxygen atoms and the energetically preferred conversion of aC ÀCd ouble or triple bond to ac arbonyl CÀOd ouble bond has been indicated as the reason for the very weak OÀOb onds. [11] The bond dissociation energies (BDE) of various alkenyl, aryl and alkynylp eroxides have been calculated, and illustrative examplesa re showni nF igure 2. [11b,c, 12] For comparison, the BDEs of some other simple peroxides are shown as well.…”

“…The bond dissociation energies (BDE) of various alkenyl, aryl and alkynyl peroxides have been calculated, and illustrative examples are shown in Figure ,. For comparison, the BDEs of some other simple peroxides are shown as well.…”

“…But even the most stable alkenyl peroxide shown here, 13 , has a much weaker O−O bond than diacyl peroxide 12 . There is no detailed information available on the decay rates of these compounds, but a computational study has estimated half‐lives on the order of seconds at ambient temperature …”

Reactive capture using metal looping: the effect of oxygen

“…Note that while it is, in principle, possible that the magnesium halide phenyl hydroperoxide salt (1) could have been converted into free phenyl hydroperoxide by the acid quench, this free phenyl peroxide is not thought to be stable in isolation, due to having low O-O bond energy, and could therefore also be directly broken down by the acid to yield phenol. 20 As mentioned in the safety section earlier in this paper, this may not be the case with potential peroxide products of other Grignard reagents and the possibility of the production of shock-sensitive and explosive alkyl hydroperoxide compounds must be considered.…”