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A Free Silanide from Nucleophilic Substitution at Silicon(II).

ABSTRACT: A computationally guided synthetic route to a free silanide derived from tris(3-methylindol-2-yl)methane ([(tmim)Si]^- ) through nucleophilic substitution on the Si^II precursor (Idipp)SiCl₂ is reported (Idipp=2,3-dihydro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron-donating properties of [(tmim)Si]^- are close to those of PMe_3. Experimentally, the [(tmim)Si]^- anion is shown to undergo clean complexation to the base metal salts CuCl and FeCl₂ , demonstrating the potential utility as a supporting ligand.

SUBMITTER: Witteman L

PROVIDER: S-EPMC6120461 | biostudies-literature | 2018 Aug

REPOSITORIES: biostudies-literature

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A Free Silanide from Nucleophilic Substitution at Silicon(II).

Witteman Léon L Evers Tim T Lutz Martin M Moret Marc-Etienne ME

Chemistry (Weinheim an der Bergstrasse, Germany) 20180430 47

A computationally guided synthetic route to a free silanide derived from tris(3-methylindol-2-yl)methane ([(tmim)Si]- ) through nucleophilic substitution on the SiII precursor (Idipp)SiCl2 is reported (Idipp=2,3-dihydro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-2-ylidene). This approach circumvents the need for strained tetrahedral silanes as synthetic intermediates. Computational investigations show that the electron-donating properties of [(tmim)Si]-</sup ...[more]

PMID: 29577491

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