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

doi:10.1021/acs.inorgchem.6b01716

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 journal › Article › peer-review

45 Citations (Scopus)

Abstract

The cyclic alkyl(amino) carbene (cAAC) 1 reacted with SiI₄ in toluene, affording the cAAC-silicon tetraiodide complex [(cAAC_Me)SiI₄] (2, cAAC_Me =: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 [(cAAC_Me)SiI₂] (3). DFT calculations show that the C_carbene-Si bond in 3 is formed by the donation of the lone pair of electrons on the C_carbene atom to the SiI₂ moiety, while the π-back-bonding of the lone pair of electrons on the Si atom to the C_carbene 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 [(cAAC_Me)Si(NSiMe₃)I₂] (4). Compound 3 reacted with I_iPrMe (:C{N(iPr)CMe}₂) in n-hexane to form the NHC-cAAC-silyliumylidene iodide [cAAC_Me(SiI)I_iPrMe]I (5), which was then reacted with two equivalents of KC₈ in toluene to furnish [cAAC_MeSi(I_iPrMe)] (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 cAAC_Me and I_iPrMe. Compounds 3-6 were elucidated by NMR spectroscopy, X-ray crystallography, and theoretical studies.

Original language	English
Pages (from-to)	9091-9098
Number of pages	8
Journal	Inorganic Chemistry
Volume	55
Issue number	17
DOIs	https://doi.org/10.1021/acs.inorgchem.6b01716
Publication status	Published - Sept 6 2016
Externally published	Yes

Bibliographical note

Publisher Copyright:
© 2016 American Chemical Society.

ASJC Scopus Subject Areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{e3e3f655317f46feae8f69a1828bb1c4,

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

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.",

author = "Yan Li and Chan, {Yuk Chi} and Yongxin Li and Indu Purushothaman and Susmita De and Pattiyil Parameswaran and So, {Cheuk Wai}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

year = "2016",

month = sep,

day = "6",

doi = "10.1021/acs.inorgchem.6b01716",

language = "English",

volume = "55",

pages = "9091--9098",

journal = "Inorganic Chemistry",

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TY - JOUR

T1 - Synthesis of a Bent 2-Silaallene with a Perturbed Electronic Structure from a Cyclic Alkyl(amino) Carbene-Diiodosilylene

AU - Li, Yan

AU - Chan, Yuk Chi

AU - Li, Yongxin

AU - Purushothaman, Indu

AU - De, Susmita

AU - Parameswaran, Pattiyil

AU - So, Cheuk Wai

PY - 2016/9/6

Y1 - 2016/9/6

N2 - 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.

AB - 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.

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 17

ER -

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

Abstract

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