Journal of Physical Chemistry A, Vol.108, No.37, 7548-7553, 2004
Ionic reactions between formaldehyde and hydrocarbons. H-2 transfer as a hydrogenation mechanism in astrochemistry
Hydrogen transfer is a major channel in the ionized C2H2+/H2CO and H2CO+/C2H2 reaction systems, producing C2H4+ + CO. Similarly, H-2 transfer from H2CO is observed in reactions of the ions C3H3+ (linear), CH3CCH+, H2CCCH2+, C3H5+, and HCCCCH+ with formaldehyde, resulting in hydrogenated hydrocarbon ions. The energetics of these reactions allow a two-step mechanism of H+ or H transfer forming a distonic (BH+HCO) complex, followed by H transfer to form BH2+. Ab initio calculations on the acetylene/formaldehyde system show that the reaction can proceed through a stable cyclic adduct, dissociating to yield C2H4+ that contains carbon atoms from both acetylene and formaldehyde. Both experiment and theory show that H2CO+ does not react with hydrogen, making it a stable reactant ion in interstellar chemistry. The reactions where either H-2(+) or H-2 is transferred can provide significant pathways for the hydrogenation of unsaturated hydrocarbons in interstellar clouds. The reactions of three C2Hx+, (x = 0, 1, or 2) species with acetaldehyde are also reported.