Contributions to the chemistry of silicon–nitrogen compounds. Part CVIII. Nuclear magnetic resonance kinetic study of the synthesis of tris(trimethylsilyl)amine

Abstract

The rates of reaction of metal derivatives of hexamethyldisilazane (M = Li, Na) with trimethylsilyl halides and pseudohalides (X = Cl, I, NC)[(Me₃Si)₂NM + XSiMe₃→ MX + N(SiMe₃)₃] have been studied by n.m.r. spectroscopy in benzene and ether solution. They are in the following order for different M, X, and solvent: Na > Li; NC > I Cl; C₆H₆ [graphic omitted] Et₂O. For the reactions of Me₃SiCN in benzene solution, evidence was obtained for formation of a complex between the reactants at an intermediate stage in the reaction. Bis(trimethylsilyl)sodium amide and trimethylsilyl iodide give tris(trimethylsilyl)amine in benzene solution with high yield at 20 °C in only 10 min. Trimethylsilyl cyanide reacts much faster with lithium bis(trimethylsilyl)amide than with pentacarbonyliron.