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Download file1,3-Diphospha-2-silaallylic Lithium Complexes and Anions: Synthesis, Crystal Structures, Reactivity, and Bonding Properties
journal contribution
posted on 1998-05-13, 00:00 authored by Dirk Lange, Elke Klein, Holger Bender, Edgar Niecke, Martin Nieger, Rudolf Pietschnig, Wolfgang W. Schoeller, Henri RanaivonjatovoTrichlorosilanes RSiCl3 (R = t-Bu, Mes, Cp*, Is,
OAr) reacted with a 4-fold excess of lithium
phosphanide ArPHLi (Ar =
2,4,6-tBu3C6H2) to
form 1,3-diphospha-2-silaallylic complexes
3a−f. From the latter, the corresponding
free allylic anions could be liberated by
complexation of the lithium cation with [15]-crown-[5], as could be
established on the basis
of NMR spectra and X-ray structures. In addition, the bonding in
the Li complexes was
further investigated using ab initio calculations of double-ξ
quality. The influence of cation
solvation on the complex geometry was explored as well. The
chemical reactivity of 1,3-diphospha-2-silaallylic anions with electrophiles (E =
H+, ClPR‘R‘‘) was investigated. 1,3-Diphospha-2-silapropenes 4a−d and
1,3,4-triphospha-2-silabutenes-(1) 5a−e and
6a were
prepared.
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Keywords
Bonding Properties Trichlorosilanes RSiCl 3cation solvationBuOArSynthesichemical reactivityAnionlithium phosphanide ArPHLiLi complexesMecomplexationComplexeDiphosphaallylic anionsReactivityCrystal StructuresdiphosphabasisClPRab initio calculationsNMR spectraCpinfluencetriphosphaLithiumlithium cationlatterelectrophile