19Si and 13C NMR studies of organosilicon chemistry. VI. Chemical shifts, coupling constants, and relaxation times for Me3SiSMe and (Me3Si)3N

Harris, Robin K.; Lemarié, Bernard

doi:10.1016/0022-2364(76)90223-7

Cited by 9 publications

(1 citation statement)

References 14 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…A linear relationship between 13C and nB shielding values of isoelectronic and isostructural molecules was demonstrated. ^Si and CMR studies of the chemical shifts, coupling constants and relaxation times for Me3SiSMe and (Me3Si)3N have been described (176). Proton-decoupled 19F and ^P NMR spectra of a series of dialkyltetafluorodiphosphetidines, (RF2PNMe)2, have been recorded (177) and analyzed for temperatures high enough for gauchetrans exchange to be rapid on the NMR time scale and at low temperatures when exchange is slow.…”

Section: Inorganicmentioning

confidence: 99%

Nuclear magnetic resonance spectrometry

Wasson¹,

Corvan²

1978

Anal. Chem.

View full text Add to dashboard Cite

Section: Inorganicmentioning

confidence: 99%

Nuclear magnetic resonance spectrometry

Wasson¹,

Corvan²

1978

Anal. Chem.

View full text Add to dashboard Cite

²⁹Si NMR Experiments in Solutions of Organosilicon Compounds

Schraml

2009

Patai's Chemistry of Functional Groups

View full text Add to dashboard Cite

show abstract

Preparative, spectroscopic, and structural studies on some new silylamines

et al. 1993

View full text Add to dashboard Cite

The synthesis and characterization of two complete series of trimethylsilane. Crystal structure analyses reveal that dibenbenzyl(phenylsily1)amines (PhHzSi),(PhH2C)3 -,N, benzyl(p-zyl(p-tolylsily1)amine (7) and 10 contain planar nitrogen atoms. tolylsily1)amines (p-H3CC6H4H2Si),(PhHzC)3 -,N, and of bis-Heteronuclear NMR spectra ('H, I3C, I5N, and "Si) have been (p-tolylsily1)amine are described. The compounds have measured for all compounds. The 15N chemical shifts are been prepared from the corresponding arnines and chlorosishown to be sensitive to variations of the geometry at the lanes with triethylamine as the auxiliary base. Bis(pheny1si-nitrogen atom. The coupling constants 1J('5Nz9Si ) show a linlyl)(trimethylsilyl)amine, (PhH2Si),NSiMe3 (lo), was obtained ear correleation with the N-Si bond lengths.by the reaction of lithium bis(phenylsily1)amide with chloro-The planarity of nitrogen coordination in silylamines continues to be a frequently discussed issue [']. This unique structural feature -as compared to the carbon analogs -was first discovered for trisilylamine, (H3Si)3N, in a gas-phase electron diffraction study by Hedbergl2] in 1955 and confirmed for the crystalline state by Barrow and Ebsworth in 1984[31. All doubly and triply silylated amines whose structures have been elucidated are planar at nitrogen r41. It is only for selected monosilylated amines, like dimethylsilylamine, (H3C)2NSiH3r that pyramidal nitrogen has been observed in the gas phaseL5]. In the crystalline phase, (H3S& NCH3 is associated to give pentamers with tetrahedral coordination at nitrogen and trigonal-bipyramidal coordination at siliconL6]. These results have prompted a large number of theoretical studies [',*]. In a series of calculations the configurational effect in the Si3N, Si,NC, and SiNC2 units has been interpreted initially in terms of d-orbital participation [(p+d)n bonding], but a more sophisticated treatment has shown that such contributions should be only marginal. Other approaches have focused on o/n-hyperconjugative effects and on electrostatic effects originating from the special force field for longer bond distances and higher polarity of SiN as compared to CN linkages, and on steric effects. All of these studies agree with the prediction that the inversion barrier at nitrogen -if any -should be flat and that only a few kJ/mol are necessary for nitrogen inversion in silylamines. Recent findings that tertiary amines with bulky alkyl groups are also flat at nitrogen19], and that silylated primary amines R3SiNH2 appear to be pyramidal ["], have added to the current uncertainties, if not confusion.In an attempt to contribute to the discussion with more experimental data, we have described in preceding papers the synthesis and structure of tris(phenylsilyl)amine['l~lzl. In contrast to the pyramidal benzylamine analog['91, this molecule has been shown to be completely planar at nitrogen. Since there is no reason to invoke steric effects for (PhH2Si)3N with six small hydrogen substituents at the silicon atoms and virt...

show abstract

19Si and 13C NMR studies of organosilicon chemistry. VI. Chemical shifts, coupling constants, and relaxation times for Me3SiSMe and (Me3Si)3N

Cited by 9 publications

References 14 publications

Nuclear magnetic resonance spectrometry

Nuclear magnetic resonance spectrometry

²⁹Si NMR Experiments in Solutions of Organosilicon Compounds

Preparative, spectroscopic, and structural studies on some new silylamines

Contact Info

Product

Resources

About

19Si and 13C NMR studies of organosilicon chemistry. VI. Chemical shifts, coupling constants, and relaxation times for Me3SiSMe and (Me3Si)3N

Cited by 9 publications

References 14 publications

Nuclear magnetic resonance spectrometry

Nuclear magnetic resonance spectrometry

29Si NMR Experiments in Solutions of Organosilicon Compounds

Preparative, spectroscopic, and structural studies on some new silylamines

Contact Info

Product

Resources

About

²⁹Si NMR Experiments in Solutions of Organosilicon Compounds