通过O、S或P配体的分子内配位作用实现有机硅鎓离子的稳定化

Stabilization of Organosilicenium Ions by means of Intramolecular Coordination of O, S, or P Ligands.

作者信息

Berlekamp Uwe-H, Jutzi Peter, Mix Andreas, Neumann Beate, Stammler Hans-Georg, Schoeller Wolfgang W

机构信息

Fakultät für Chemie der Universität, Universitätsstrasse 25, D-33615 Bielefeld (Germany), Fax: (+49) 521-106-6026.

Fakultät für Chemie der Universität Bielefeld (Germany).

出版信息

Angew Chem Int Ed Engl. 1999 Jul 12;38(13-14):2048-2050. doi: 10.1002/(SICI)1521-3773(19990712)38:13/14<2048::AID-ANIE2048>3.0.CO;2-C.

DOI:10.1002/(SICI)1521-3773(19990712)38:13/14<2048::AID-ANIE2048>3.0.CO;2-C

PMID:34182665

Abstract

For the intramolecular stabilization of silicenium ions (RSi), O, S, and P donors as well as the known nitrogen-containing systems (as in 1 a) are suitable. The silyl cations in 1 a-d show a trigonal-bipyramidal structure; dynamic processes can be proved by NMR spectroscopy for 1 c, d. Calculations on model compounds document substantial differences in the bonding relationships and support the structural findings. Furthermore, preliminary experiments with 1 b-d indicate significant differences in reactivity.

摘要

对于硅鎓离子（RSi）的分子内稳定作用，氧、硫、磷供体以及已知的含氮体系（如在1 a中）是合适的。1 a - d中的甲硅烷基阳离子呈现三角双锥结构；通过核磁共振光谱法可以证明1 c、d存在动态过程。对模型化合物的计算表明键合关系存在显著差异，并支持结构研究结果。此外，对1 b - d的初步实验表明反应性存在显著差异。