CH3+ is the most trivial carbocation, but are its heavier congeners just lookalikes?

被引:40
作者
Kapp, J [1 ]
Schreiner, PR [1 ]
Schleyer, PV [1 ]
机构
[1] UNIV ERLANGEN NURNBERG, INST ORGAN CHEM, CTR COMP CHEM, D-91054 ERLANGEN, GERMANY
关键词
D O I
10.1021/ja962275d
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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.
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收藏
页码:12154 / 12158
页数:5
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