ABSTRACT
The reactions of 1-tetradecene and 1-pentadecene, the C14 and C15 linear 1-alkenes, with OH radicals in the presence of NOx were investigated in a series of environmental chamber experiments. Particle-phase ß-hydroxynitrates, dihydroxynitrates, dihydroxycarbonyls, and 1,4-hydroxynitrates and gas-phase aldehydes were sampled and then identified and quantified using a suite of offline analytical techniques that included derivatization, gas and liquid chromatography, and multiple types of mass spectrometry. Measured molar yields of products formed by OH radical addition to the CâC double bond, including ß-hydroxynitrates, dihydroxynitrates, dihydroxycarbonyls (which have not been previously directly quantified with high accuracy), and aldehydes were 0.125 ± 0.01, 0.048 ± 0.005, 0.240 ± 0.04, and 0.268 ± 0.03 (0.264 ± 0.02 and 0.271 ± 0.04 for the formaldehyde and tridecanal/tetradecanal co-products of ß-hydroxyalkoxy radical decomposition), respectively. These values give a total molar yield of 0.681 ± 0.05, which agrees very well with the results of kinetics measurements that indicate that the fraction of reaction that occurs by OH radical addition is 0.70. The yields were used to calculate branching ratios for all OH radical addition pathways, including a value of 0.18 for the formation of dihydroxynitrates from the reaction of dihydroxyperoxy radicals with NO and values of 0.47 and 0.53 for ß-hydroxyalkoxy radical decomposition and isomerization. The results were used with literature data on the yields of aldehydes measured for similar reactions of smaller alkenes, a model for the effect of carbon number on branching ratios for organic nitrate formation, and a mechanism for H atom abstraction derived from studies of linear alkanes to achieve a complete, quantitative gas-phase reaction mechanism for 1-alkenes. The results should also be useful for constructing mechanisms for more complex reactions of volatile organic compounds.
ABSTRACT
The title compound, [Mo(C5H5)(C2H3O)(C12H9O3P)(CO)2], was prepared by reaction of [Mo(C5H5)(CO)3(CH3)] with tris-(furan-2-yl)phosphane. The Mo(II) atom exhibits a four-legged piano-stool coordination geometry with the acetyl and phosphine ligands trans to each other. The O atom of the acetyl ligand points down, away from the Cp ring. In the crystal, mol-ecules form centrosymmetrical dimers via π-π inter-actions between furyl rings [the centroid-centroid distance is 3.396â (4)â Å]. The dimers are linked by C-Hâ¯O hydrogen bonds into layers parallel to (100).
