2009-12-24
The reaction of the acrylonitrile ion CH2{double bond, long}CH-C{triple bond, long}N{radical dot}+ with HCN: Proton-transport catalysis vs formation of ionized pyrimidine
Publication
Publication
Chemical Physics Letters , Volume 482 - Issue 4-6 p. 211- 216
The CBS-QB3 model chemistry predicts that the title ion-molecule reaction, of potential interest in astrochemistry, yields a stable head-to-tail dimer, [HC{double bond, long}N-CH2C(H)C{triple bond, long}N]{radical dot}+(D1). Cyclization of D1 into ionized pyrimidine seems possible, but the initiating 1,2-H shift is close in energy to back-dissociation into CH2{double bond, long}C(H)CN{radical dot}+(AN) + HCN. Less energy demanding is formation of the H-bridged isomers [CH2{double bond, long}C(CN)H--N{triple bond, long}CH]{radical dot}+and [HC{triple bond, long}N--HC(H){double bond, long}C(H)CN]{radical dot}+, whose HCN component may catalyze isomerization of AN into CH2{double bond, long}C{double bond, long}C{double bond, long}NH{radical dot}+(AN1) and CH{double bond, long}C(H)C{double bond, long}NH{radical dot}+(AN2) respectively. Tandem mass spectrometry based experiments using15N/13C labelling show that cyclization of D1 does not occur and that AN1 is the predominant reaction product instead.
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| doi.org/10.1016/j.cplett.2009.10.017, hdl.handle.net/1765/24310 | |
| Chemical Physics Letters | |
| Organisation | Erasmus MC: University Medical Center Rotterdam |
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Ervasti, H., Jobst, K., Gerbaux, P., Burgers, P., Ruttink, P., & Terlouw, J. (2009). The reaction of the acrylonitrile ion CH2{double bond, long}CH-C{triple bond, long}N{radical dot}+ with HCN: Proton-transport catalysis vs formation of ionized pyrimidine. Chemical Physics Letters, 482(4-6), 211–216. doi:10.1016/j.cplett.2009.10.017 |
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