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An Isolable Silicon Dicarbonate Complex from Carbon Dioxide Activation with a Silylone
Author(s) -
Burchert Alexander,
Yao Shenglai,
Müller Robert,
Schattenberg Caspar,
Xiong Yun,
Kaupp Martin,
Driess Matthias
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201610498
Subject(s) - chemistry , carbene , ligand (biochemistry) , silicon , monomer , thermochemistry , lewis acids and bases , carbon dioxide , medicinal chemistry , inorganic chemistry , stereochemistry , polymer chemistry , catalysis , organic chemistry , polymer , biochemistry , receptor
The first isolable molecular silicon dicarbonate complex (bis‐NHC)Si(CO 3 ) 2 2 (bis‐NHC=H 2 C[{NC(H)=C(H)N(Dipp)}C:] 2 , Dipp=2,6‐iPr 2 C 6 H 3 ) was synthesized by facile reaction of the bis‐N‐heterocyclic carbene stabilized silylone (bis‐NHC)Si 1 , bearing a zero‐valent silicon atom, with carbon dioxide. The monomeric silicon dioxide complex (bis‐NHC)SiO 2 3 supported by the bis‐NHC ligand was proposed as a key intermediate resulting from double oxygenation of the zero‐valent silicon atom in 1 by two molar equivalents of CO 2 under liberation of CO; its subsequent Lewis acid–base reaction with CO 2 leads to 2 which has been fully characterized including an single‐crystal X‐ray diffraction analysis. Its electronic structure, spectroscopic data and the thermochemistry of the formation have been studied quantum‐chemically.