Synthesis of a Bent 2-Silaallene with a Perturbed Electronic Structure from a Cyclic Alkyl(amino) Carbene-Diiodosilylene

Yan Li, Yuk Chi Chan, Yongxin Li, Indu Purushothaman, Susmita De, Pattiyil Parameswaran*, Cheuk Wai So

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

45 Citations (Scopus)

Abstract

The cyclic alkyl(amino) carbene (cAAC) 1 reacted with SiI4 in toluene, affording the cAAC-silicon tetraiodide complex [(cAACMe)SiI4] (2, cAACMe =:C(CH2)(CMe2)2NAr, Ar = 2,6-iPr2C6H3). It further reacted with two equivalents of KC8 in toluene at room temperature to afford the first cAAC-diiodosilylene [(cAACMe)SiI2] (3). DFT calculations show that the Ccarbene-Si bond in 3 is formed by the donation of the lone pair of electrons on the Ccarbene atom to the SiI2 moiety, while the π-back-bonding of the lone pair of electrons on the Si atom to the Ccarbene atom is negligible. The presence of the lone pair of electrons on the silicon atom in 3 is also evidenced by its reaction with N3SiMe3 to form the cAAC-silaimine complex [(cAACMe)Si(NSiMe3)I2] (4). Compound 3 reacted with IiPrMe (:C{N(iPr)CMe}2) in n-hexane to form the NHC-cAAC-silyliumylidene iodide [cAACMe(SiI)IiPrMe]I (5), which was then reacted with two equivalents of KC8 in toluene to furnish [cAACMeSi(IiPrMe)] (6). The experimental and theoretical studies suggest that 6 can be described as a bent silaallene with a perturbed electronic structure, which can be attributed to the different donor-acceptor properties of cAACMe and IiPrMe. Compounds 3-6 were elucidated by NMR spectroscopy, X-ray crystallography, and theoretical studies.

Original languageEnglish
Pages (from-to)9091-9098
Number of pages8
JournalInorganic Chemistry
Volume55
Issue number17
DOIs
Publication statusPublished - Sept 6 2016
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus Subject Areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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