Momoh Paul O, Soliman Abdel-Rahman, Meot-Ner Michael, Ricca Alessandra, El-Shall M Samy
Department of Chemistry, Virginia Commonwealth University, Richmond, Virginia 23284-2006, USA.
J Am Chem Soc. 2008 Oct 1;130(39):12848-9. doi: 10.1021/ja803282c. Epub 2008 Sep 9.
We present direct evidence for low temperature associative charge transfer (ACT) reactions of acetylene onto the benzene cation that catalyze the conversion of acetylene molecules into polymerized cations and for high temperature addition/elimination reactions that lead to the generation of naphthalene-type ions. At low temperatures acetylene molecules bind noncovalently to the benzene cation, where partial charge transfer from the ion activates an acetylene molecule for addition polymerization with other associated acetylene molecules, thus amounting to catalytic cyclization/polymerization of the acetylene molecules. At high temperatures the barrier of the covalent addition of acetylene to the benzene cation to form a styrene-type ion is measured as 3.5 kcal/mol. The second acetylene addition followed by H elimination to form a naphthalene-type ion is calculated to be highly exothermic and without a barrier. These reactions can explain the formation of complex organics by gas phase ion-molecule reactions under a wide range of temperatures and pressures in astrochemical environments.
我们提供了乙炔与苯阳离子发生低温缔合电荷转移(ACT)反应的直接证据,该反应催化乙炔分子转化为聚合阳离子,以及高温加成/消除反应导致萘型离子生成的直接证据。在低温下,乙炔分子与苯阳离子非共价结合,离子的部分电荷转移激活一个乙炔分子,使其与其他缔合的乙炔分子进行加成聚合,从而实现乙炔分子的催化环化/聚合。在高温下,测得乙炔与苯阳离子共价加成形成苯乙烯型离子的势垒为3.5千卡/摩尔。计算得出,第二次乙炔加成随后消除氢形成萘型离子的反应是高度放热的且无势垒。这些反应可以解释在天体化学环境中广泛的温度和压力条件下,通过气相离子 - 分子反应形成复杂有机物的过程。