The constitution, vibrational spectra and proton resonance spectra of trimethylsilyl cyanide and isocyanide
1970; Pergamon Press; Volume: 26; Issue: 4 Linguagem: Inglês
10.1016/0584-8539(70)80283-5
ISSN1873-3824
Autores Tópico(s)Organic and Inorganic Chemical Reactions
ResumoAbstract The infrared spectrum in the region 33–4000 cm −1 , and the Raman spectra with polarization data, are reported for trimethylsilyl cyanide and isocyanide from a study of the equilibrium mixture. The infrared spectrum of normal, and 13 CN and C 15 N enriched species establishes the existence of trimethylsilyl isocyanide. An analysis of the variable temperature infrared spectrum gives Δ H 0 = 16·75 ± 0·17 kJ mol −1 for the reaction Me 3 SiCN (1) β Me 3 SiNC (1). The mole fraction of isocyanide in the liquid is only 0·0015 ± 0·0005 at 25°. A complete assignment of the vibrational spectrum of the equilibrium mixture is presented. The variable temperature proton resonance spectrum of normal and 13 CN enriched Me 3 SiCN and Me 3 SiNC, along with the 1 H( 29 Si) double resonance spectrum of the 13 CN enriched molecules, is reported. The magnetic resonance data are consistent with rapid exchange of CN groups between Me 3 SiCN and Me 3 SiNC.
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