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SF11.PNG

Solvated Silylium Cations: Structure Determination by NMR Spectroscopy and the NMR/Ab Initio/IGLO Method
By Arshadi, Mehrdad; Johnels, Dan; Edlund, Ulf; Ottosson, Carl-Henrik; Cremer, Dieter
From Journal of the American Chemical Society (1996), 118(21), 5120-5131.

Sixty R3SiX/solvent (S) and R2HSiX/S systems (R = Me, Et, Bu; X = halo, OTf, etc.; S = CH2Cl2, DMPU, DMSO, sulfolane, HMPA, MeCN, pyridine, N-methylimidazole, NEt3) were studied with the help of NMR spectroscopy for different concn. ratios of R3SiX/S and R2HSiX/S as well as different temps. With the help of measured δ29Si and δ13C chem. shifts as well as 1JSi-C and 2JSi-P coupling consts., typical NMR parameters for R3SiX and R2HSiX, R3Si(S)+, R2HSi(S)+, and R2HSi(S)2+ were established and discussed to distinguish between possible silylium cation-solvent complexes and equil. between them. Th...

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