Vibrational spectra of disilenes. Normal coordinate analysis and identification of the v(Si=Si) stretching vibration

Leites, L. A.; Bukalov, Sergey S.; Garbuzova, I. A.; West, Robert; Mangette, John E.; Spitzner, H.

doi:10.1016/s0022-328x(96)06872-6

Cited by 12 publications

(11 citation statements)

References 10 publications

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“…500-550 cm -1 . In good accord with the data, 6 Figure 1 demonstrates that the Raman spectra of 1a-c all exhibit a triplet in the region 520-550 cm -1 , which is the result of superposition of three lines, corresponding to two mesityl vibrations and to n 1 , as well as an intense line of n 2 at ca. 680 cm -1 .…”

supporting

confidence: 79%

“…15-750 cm -1 . ‡ According to a recently published paper 6 in which the normal vibrations of disilenes were analysed by normal coordinate analysis (NCA), the Si=Si stretching vibration n(Si=Si) is not localized, the Si=Si and Si-C stretching coordinates of the C 2 Si=SiC 2 moiety being heavily mixed. Their in-phase combination (n 1 ) results in a normal mode in the region 460-550 cm -1 while their out-of-phase combination (n 2 ) gives a normal mode near 700 cm -1 .…”

mentioning

confidence: 99%

“…Therefore, the assignment of the n 1 mode to the n(Si=Si) stretch and of the n 2 mode to the totally symmetric n s (Si-C) stretch is in essence arbitrary. For mesityl-substituted disilenes, the results of NCA 6 predict that two of the symmetric vibrations localized in the mesityl group should fall in the same frequency range as n 1 , i.e. 500-550 cm -1 .…”

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confidence: 99%

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Raman and UV-VIS study of the conformational polymorphism of solid tetramesityldisilene Mes2SiSiMes2

Leites

Bukalov

Mangette

et al. 1998

Mendeleev Communications

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confidence: 79%

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confidence: 99%

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Raman and UV-VIS study of the conformational polymorphism of solid tetramesityldisilene Mes2SiSiMes2

Leites

Bukalov

Mangette

et al. 1998

Mendeleev Communications

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“…33 Thus, also in the vibrational spectra of Mes 2 SidSiMes 2 and Mes(t-Bu)SidSi(t-Bu)Mes there is no normal mode which is well localized in the SidSi bond. 33 Several criteria, experimental and theoretical, point to the conclusion that the SidC double bond in 1 is significantly weaker than in the parent H 2 SidCH 2 or in other simple silenes. This is attributed mainly to the silyl substituents at the silicon end of the double bond which reduce substantially the inherent polarity of the SidC double bond.…”

Section: Discussionmentioning

confidence: 94%

The Raman, Ultraviolet, and Infrared Spectra and the J_Si_C NMR Coupling Constant of the Stable Silene (t-BuMe₂Si)(Me₃Si)Si2-Ad. Manifestations of the SiC Double Bond

et al. 2002

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The UV, preresonance Raman, and IR spectra of the stable silene t-BuMe 2 Si(Me 3 Si)Sid2-Ad (1) have been measured as well as its J SidC NMR coupling constant. The normal modes involving the ν(SidC) stretching coordinate were identified for the first time for a stable silene. The experimental data and computations of potential energy distribution and mode eigenvectors show that there is no single vibrational normal mode which can be assigned as ν(SidC). Raman intensity enhancement on approaching resonance strongly supports the conclusion that there are five lines in the region 1000-1370 cm -1 which include significant contribution from the ν(SidC) stretching coordinate. Both the SidC force constant and the J SidC NMR coupling constant (as well as the SidC bond length) indicate that the SidC bond order is smaller in 1 than that in simpler silenes of the type R 2 SidCH 2 (R ) H, Me).

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“…In the Raman spectrum the Si=Si double bond vibration occurs at 589 cm −1 (for comparison:14,15,17 Mes 2 Si=SiMes 2 : 539 cm −1 ; Mes( t Bu)Si=Si( t Bu)Mes: 522 cm −1 ; R*PhSi=SiPhR*: 592 cm −1 . See also ref 18…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure and Dehalogenation of the Disilene RClSi=SiClR [R = (tBu3Si)2MeSi]

Wibeŕg

Niedermayer

Fischer

et al. 2002

Eur. J. Inorg. Chem.

160

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The reaction of R*2MeSi−SiX2X′ (X/X′ = Cl/Br, Br/Cl) with NaR* (R* = supersilyl SitBu3) leads, probably via the silylenes R*2MeSi−SiX, to the trans‐configurated disilene (R*2MeSi)ClSi=SiCl(SiMeR*2), which could be isolated as orange‐red crystals. According to an X‐ray structure analysis, the central SiClSi=SiClSi framework of the disilene − the formation mechanisms of which are discussed − is planar. The Si=Si double bond is as short as 2.163(4) Å and shows a band in the Raman spectrum at 589 cm−1. Due to its insolubility in organic solvents, no NMR spectra of the disilene in solution were obtained. The spatially overcrowded disilene is stable towards H2O, MeOH, HF, and NaR*. It melts at 228 °C with decomposition. Reduction of the disilene occurs with LiC10H8 in THF with formation of a reaction mixture containing a chlorine‐free product that gives a low field 29Si NMR signal at δ = 91.5 (the region for unsaturated Si atoms). It transforms in solution with traces of oxygen into a substance which, according to mass spectrometry (chemical ionization), shows a mass for the disilyne R*2MeSi−Si≡Si−SiMeR*2 plus two oxygen atoms. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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Vibrational spectra of disilenes. Normal coordinate analysis and identification of the v(Si=Si) stretching vibration

Cited by 12 publications

References 10 publications

Raman and UV-VIS study of the conformational polymorphism of solid tetramesityldisilene Mes2SiSiMes2

Raman and UV-VIS study of the conformational polymorphism of solid tetramesityldisilene Mes2SiSiMes2

The Raman, Ultraviolet, and Infrared Spectra and the J_Si_C NMR Coupling Constant of the Stable Silene (t-BuMe₂Si)(Me₃Si)Si2-Ad. Manifestations of the SiC Double Bond

Synthesis, Structure and Dehalogenation of the Disilene RClSi=SiClR [R = (tBu3Si)2MeSi]

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Vibrational spectra of disilenes. Normal coordinate analysis and identification of the v(Si=Si) stretching vibration

Cited by 12 publications

References 10 publications

Raman and UV-VIS study of the conformational polymorphism of solid tetramesityldisilene Mes2SiSiMes2

Raman and UV-VIS study of the conformational polymorphism of solid tetramesityldisilene Mes2SiSiMes2

The Raman, Ultraviolet, and Infrared Spectra and the JSiC NMR Coupling Constant of the Stable Silene (t-BuMe2Si)(Me3Si)Si2-Ad. Manifestations of the SiC Double Bond

Synthesis, Structure and Dehalogenation of the Disilene RClSi=SiClR [R = (tBu3Si)2MeSi]

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The Raman, Ultraviolet, and Infrared Spectra and the J_Si_C NMR Coupling Constant of the Stable Silene (t-BuMe₂Si)(Me₃Si)Si2-Ad. Manifestations of the SiC Double Bond