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[交流] [J. Am. Chem. Soc.] A Unique Transition Metal-Stabilized Silicon Cation

JACS的一篇大作，有兴趣的看看啊
A Unique Transition Metal-Stabilized Silicon Cation

Kristine Mther†, Roland Frhlich†‡, Christian Mck-Lichtenfeld†§, Stefan Grimme†§, and Martin Oestreich*†
†Organisch-Chemisches Institut, ‡Rntgenstrukturanalyse, and §Theoretische Organische Chemie, Westflische Wilhelms-Universitt Mnster, Corrensstrasse 40, 48149 Mnster, Germany
J. Am. Chem. Soc., Article ASAP
DOI: 10.1021/ja205538t
Publication Date (Web): July 19, 2011
Copyright © 2011 American Chemical Society
martin.oestreich@uni-muenster.de

Abstract

Trivalent silicon cations are exceptionally strong electron pair acceptors that react, either desired or undesired, with almost any σ and π basic molecule. One way of intramolecular attenuation of the Lewis acidity of these superelectrophiles is by installation of a ferrocene unit at the electron-deficient silicon atom. While well-understood for isoelectronic α-ferrocenyl-substituted carbenium ions and also boranes, the stabilizing interactions between the ferrocene backbone and a positively charged silicon atom are not clear due to the challenge of crystallizing such cations. The structural characterization of our ferrocene-stabilized silicon cation now reveals an unprecedented bonding motif different from its analogues. An extreme dip angle of the silicon atom toward the iron atom is explained by two three-center-two-electron (3c2e) bonds through participation of both the upper and the lower aromatic rings of the ferrocene sandwich structure. The positive charge is still localized at the silicon atom that also retains a quasi-planar configuration.

https://pubs.acs.org/doi/abs/10.1021/ja205538t

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