Reaction of the Excited Oxygen Atoms O(1D2) with Neopentane

The reaction of $\mathrm{O}{(}^1{D}_2)$ atoms, formed by photolysis of N₂O at 2139 Å, with neopentane, has been studied at room temperature in the gas phase at total pressures from 5 to 1300 torr. The main features of the reaction are similar to those observed previously in this Laboratory with propane and isobutane. The reaction proceeds mainly along two paths: (a) insertion of $\mathrm{O}{(}^1{D}_2)$ into the CH bonds of neopentane to form vibrationally excited (“hot”) neopentanol accounts for about 66% of the total reaction, and (b) abstraction of hydrogen from neopentane to form neopentyl radicals and OH accounts for about 25% of the reaction. The “hot” neopentanol is stabilized at pressures much lower than those required for stabilization of the “hot” butanols. The mean lifetime of the “hot” neopentanol has been determined and is found to be 4.2 × 10⁻⁹ sec. The reaction mechanism is discussed.