Movatterモバイル変換

[0]ホーム
URL:

Jump to content
WikipediaThe Free Encyclopedia
Search

Silanone

From Wikipedia, the free encyclopedia
Silicon analogue of a ketone
The general structure of a silanone

Asilanone inchemistry is thesilicon analogue of aketone. The general description for this class oforganic compounds is R1R2Si=O, with silicon connected to a terminaloxygen atom via adouble bond and also with twoorganic residues (R).[1] Silanones are extremely reactive[1] and until 2013 were only detected by argonmatrix isolation[2][3] or in the gas phase[4] but not isolated. A synthesis of a stable silanone was reported in 2014. Silanones are of some interest to academic research, with their reactivity being of some relevance to thedouble bond rule.

Silanones are unstable and favoroligomerisation tosiloxanes. The reason for this instability is the weakpi bond with a smallHOMO–LUMO energy gap caused by an unfavorable overlap between the p-orbitals of silicon and oxygen. A second reason for the observed instability is the stronglypolarizedsilicon–oxygen bond, Siδ+–Oδ−.[1]

History

[edit]

The first to postulate a silanone were Kipping & Lloyd in 1901,[5] but their products were in fact siloxanes. It was not until 2014 that a stable silanone was reported.[6] In this compound, silicon is bonded to a SIDipp (1,3-bis(2,6-iPr2-C6H3)imidazolidin-2-ylidene) group and a (Cp*)Cr(CO)3 group. Its stability is owed to the direct coordination of silicon tochromium and tosteric shielding. The reported Si=Obond length is 1.526Å, in line with expectations. It has been described as acationic metallosilanone.[1]

Other strategies have recently been used to stabilise silanones,[7] for example coordination toLewis acids or bases[8] andsteric shielding.[9]

References

[edit]
  1. ^abcdSen, S. S. (2014). "A Stable Silanone with a Three-Coordinate Silicon Atom: A Century-Long Wait is Over".Angew. Chem. Int. Ed.53 (34):8820–8822.doi:10.1002/anie.201404793.PMID 24990653.
  2. ^On the proposed thermal interconversion of matrix-isolated dimethylsilylene and 1-methylsilene: their reactions with oxygen atom donors Charles A. Arrington, Robert West, Josef Michl J. Am. Chem. Soc.,1983, 105 (19), pp 6176–6177doi:10.1021/ja00357a048
  3. ^Infrared spectroscopic evidence for silicon-oxygen double bonds: silanone and the silanoic and silicic acid molecules Robert Withnall, Lester Andrews J. Am. Chem. Soc.,1985, 107 (8), pp 2567–2568doi:10.1021/ja00294a070
  4. ^M. Bogey; B. Delcroix; A. Walters; J-C Guillemin (1996). "Experimentally Determined Structure of H2SiO by Rotational Spectroscopy and Isotopic Substitution".J. Mol. Spectrosc.175 (2):421–428.Bibcode:1996JMoSp.175..421B.doi:10.1006/jmsp.1996.0048.
  5. ^XLVII.—Organic derivatives of silicon. Triphenylsilicol and alkyloxysilicon chlorides F. Stanley Kipping, Ph.D., D.Sc., F.R.S. and Lorenzo L. Lloyd J. Chem. Soc., Trans., 1901,79, 449-459doi:10.1039/CT9017900449
  6. ^Filippou, A. C., Baars, B., Chernov, O., Lebedev, Y. N. and Schnakenburg, G. (2014),Silicon–Oxygen Double Bonds: A Stable Silanone with a Trigonal-Planar Coordinated Silicon Center. Angew. Chem. Int. Ed., 53: 565–570.doi:10.1002/anie.201308433
  7. ^Xiong, Y.; Yao, S.; Driess, M. (2013). "Chemical Tricks To Stabilize Silanones and Their Heavier Homologues with EO Bonds (E=Si–Pb): From Elusive Species to Isolable Building Blocks".Angew. Chem. Int. Ed.52 (16):4302–4311.Bibcode:2013ACIE...52.4302X.doi:10.1002/anie.201209766.PMID 23450830.[clarification needed]
  8. ^Sun, T.; Li, J.; Wang, H. (2022). "Recent Advances in the Chemistry of Heavier Group 14 Analogues of Carbonyls".Chem. Asian J.17 (18) e202200611.doi:10.1002/asia.202200611.PMID 35883252.S2CID 251104394.
  9. ^Kobayashi, Ryo; Ishida, Shintaro; Iwamoto, Takeaki (2019)."An Isolable Silicon Analogue of a Ketone that Contains an Unperturbed Si=O Double Bond".Angew. Chem. Int. Ed.58 (28):9425–9428.Bibcode:2019ACIE...58.9425K.doi:10.1002/anie.201905198.PMID 31095845.S2CID 157056381.
Retrieved from "https://en.wikipedia.org/w/index.php?title=Silanone&oldid=1319849789"
Category:
Hidden categories:
[8]ページ先頭
©2009-2025 Movatter.jp