Nitrogen-silicon bonds reactions with

Nitrogen-silicon bonds. The reaction of ethylenimine with chlorosil nee gives products in which the axiridine ring is attached to ailioon. 7... 

Recent advances in the Staudinger reaction of tertiary phosphines with azido compounds have been reviewed.The reaction of the alkynylphosphine (88) with phenylazide yields the unstable intermediate (89), which in the presence of protic substances undergoes nucleophilic addition to the triple bond. The reactivity of the nitrogen-silicon bond of the phosphinimine derived from triphenylphosphine and trimethylsilylazide has been exploited in reactions with chloroformyl reagents to generate new functionalised phosphinimines, e.g., (90). ... 

The reaction involves initial insertion of sulfur trioxide into the nitrogen-silicon bond of anilinotrimethylsilane 466 the sulfamic acid 467 was, however, contaminated with small amounts of anilinium salts. It was discovered that the reaction of anilinotrimethylsilane 466 with trimethylsilyl chlorosulfonate 459 gave improved yields of the pure sulfamic acid 467. Trimethylsilyl chlorosulfonate 459 will effect the sulfosilation of aromatic hydrocarbons to give the trimethylsilyl arenesulfonates 468 (Equation 148). 

Interestingly, this ligand type is not new and was previously been described by Roesky and co-workers (209) from the reactions of TiX4 (X = Cl, Br) with Me2NC(S)SN(SiMe3)2, a result of the cleavage of both nitrogen-silicon bonds (Eq. 209). 

Another modification of the double silylation process reported by Tanaka and co-workers involves the use of a bis(hydrosilane) instead of a disilane as the reactant molecule.61 This reaction can be described as a dehydrogenative double silylation, in that two Si-H bonds are activated rather than an Si-Si bond. The system is best catalyzed by Pt(CH2=CH2)(PPh3)2 other Pt, Pd, Ru, and Rh complexes give only very low yields of the double-silylated products. Alkynes, alkenes, and dienes undergo reaction with the bis (hydrosilane) with a range of results. Silicon-oxygen bonds and silicon-nitrogen bonds can also be formed by this method and are discussed in the appropriate sections later. 

Insertion of the Si=N bond into polar bonds is the most used reaction for the characterization of very reactive and transient silanimines. Especially, the reaction with alcohols is often the first reaction to be carried out with silicon-nitrogen multiple bond systems. Other reagents used for insertion reactions are amines, water and alkoxysilanes (equation 269)300,303,306,311,351-353. The insertion into E—X bonds (E = Si, Ge, Sn X = Cl, OR, NR2, N3) has been shown earlier in this review for the insertion into the Si—N bond of silyl azides310,351. A reaction reported is the insertion of 678 into the C—H... 

Amino, alkoxy, and aryloxy polyphosphazenes are typically prepared by nucleophilic displacement reactions of poly(dihalophosphazenes). Analogous reactions with organometallic reagents, however, result in chain degradation and cross linking rather than in linear, alkyl, or aryl substituted poly(phosphazenes). The thermolysis of appropriate silicon-nitrogen-phosphorus compounds can be used to prepare fully P—C bonded poly(organophosphazenes). The synthesis of two of these materials and their Si—N—P precursors is described here. 

In our group we decided to investigate the above mentioned reaction with the stable and monomeric permethylsilicocene. We used LXe and LN2 as totally transparent solvents for IR spectroscopy and were therefore able to characterize the reversible adduct formation with carbon monoxide and nitrogen [4]. The coordinated nitrogen absorbs at 2053 cm", which is value observed in common d-metal nitrogen complexes. For the silicon carbonyl (2065 cm" ) again a back bonded CO is observed, but it is weaker than in Me2SiCO. 

The manufacture of reaction-bonded Si3N4 begins with a preform of silicon. This preform is nitrided in an atmosphere of pure nitrogen or of nitrogen/hydrogen. The reaction proceeds without volume change, but the products have a minimum porosity of 10%. 98% of the theoretical density can be achieved by postsintering. 

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