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...
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structure structure (organic substances) K 9000 -050Solid-State Structure of Tris(phenylsilyl)amine -(X-ray diffraction analysis). -(MITZEL, N.; SCHIER, A.; SCHMIDBAUR, H.; Chem.
ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.
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