Journal article

Authors list: Kapp, J; Schreiner, PR; Schleyer, PV

Publication year: 1996

Pages: 12154-12158

Journal: Journal of the American Chemical Society

Volume number: 118

Issue number: 48

ISSN: 0002-7863

DOI Link: https://doi.org/10.1021/ja962275d

Publisher: American Chemical Society

Abstract: 

While the strongly bound D-3h AH(3)(+) cations are favored energetically for CH3+ and SiH3+, C-s HA(+)... H-2 complexes are computed to be the global minima for A = Sn and Pb. The structures, relative energies, and dissociation limits (D-o) of the AH(3)(+) cations (A = C, Si, Ge, Sn, and Pb) were studied at the Becke3LYP density functional level [6-311++G(2d,2p) basis sets for C, Si, and Ge, (quasi)relativistic effective core potentials with TZ+2P valence basis sets for Sn and Pb]. The SiH3+ potential energy surface computed for calibration at the CCSD(T) lever is in very good quantitative agreement with the Becke3LYP results. The AH(3)(+)-->HA(+)... H-2 rearrangement illustrates the rare case where two transition states are connected directly (one high-lying, 45-58 kcal mol(-1) vs D-3h AH(3)(+) and one lower in energy, 0-37 kcal mol(-1)) without an intervening minimum. Due to the appreciable D-o values for both the AH(3)(+) and the HA(+)... H-2 species, they should be experimentally verifiable.

Harvard Citation style: Kapp, J., Schreiner, P. and Schleyer, P. (1996) CH3+ Is the Most Trivial Carbocation, but Are Its Heavier Congeners Just Lookalikes?, Journal of the American Chemical Society, 118(48), pp. 12154-12158. https://doi.org/10.1021/ja962275d

APA Citation style: Kapp, J., Schreiner, P., & Schleyer, P. (1996). CH3+ Is the Most Trivial Carbocation, but Are Its Heavier Congeners Just Lookalikes?. Journal of the American Chemical Society. 118(48), 12154-12158. https://doi.org/10.1021/ja962275d