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IPr 3 Si 3 Cl 5 + : A Highly Reactive Cation with Silanide Character
Author(s) -
Uhlemann Fabian,
Schnepf Andreas
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601728
Subject(s) - halogenation , carbene , chemistry , steric effects , dichloromethane , silylation , deuterium , salt (chemistry) , halogen , reactive intermediate , silicon , halide , medicinal chemistry , reagent , inorganic chemistry , stereochemistry , organic chemistry , catalysis , physics , alkyl , quantum mechanics , solvent
The reaction of a metastable SiCl 2 solution with the sterically less‐demanding carbene N , N ‐diisopropylimidazo‐2‐ylidene (IPr) yields the salt [(IPr 3 Si 3 Cl 5 ) + ]Cl − ( 1 ‐Cl), containing a silyl cation with a Si 3 backbone. Salt 1 is highly reactive, but it can be used as a reagent in deuterated dichloromethane, whereby dehalogenation with Me 3 SiOTf (OTf=O 3 SCF 3 ) gives the dicationic silyl halide [(IPr 3 Si 3 Cl 4 )] 2+ 2 . Quantum chemical calculations show that the HOMO is localized at the negatively charged central silicon atom of 1 and 2 , and thus although both compounds are cations they are better described as silanides, which was also corroborated by NMR investigations.