Abstract Tri-tert-butylsiloxane compounds of transition metals are obtained by two different routes, one of these involves condensation of tri-tert-butylsilanol with the binary oxides V2O5, CrO3, MoO3, and Re2O7, while the other proceeds via a similar reaction between the chlorides VOCl3, NbCl5, TaCl5, CrO2Cl2, and the silanol. The new compounds, having good thermal stability and remarkable resistence to hydrolysis, are characterized by IR, 1H NMR, and mass spectra.

Die sterisch überladenen Disiloxane (III) bzw. (VI) werden erhalten bei der Suche nach einfacheren Synthesewegen für das Silandiol (II) bzw. Silanol (V) durch Reaktion der Silane (I) bzw. (IV) mit AgNO3 im Überschuß.

No abstract

The overcrowded molecules 1,1,3,3-tetra-tert-butyldisiloxane-1,3-diol (2) and penta-tertbutyldisiloxanol (4) have been obtained during the attempted synthesis of tri-tert-butylsilanol and di-tert-butylsilanediol by reaction of tri-tert-butylsilane and di-tert-butylchlorosilane, resp., with silver nitrate. Compounds 2 and 4 were also formed either by condensation of two molecules of di-tert-butylsilanediol or by co-condensation of the silanediol with tri-tert-butylsilanol in the presence of jo-toluenesulfonic acid. Reactions of tri-tert-butylsilanol with silicon tetrachloride yielded 1,1,1,5,5,5-hexa-tert-butyl-3,3-dichlorotrisiloxane.

Abstract Tri-tert-butylchlorosilane reacts with potassium pseudohalides in the presence of catalytic amounts of the crown ether 18-crown-6 to give the tri-tert-butylsilicon pseudo-halides (t-C4H9)3SiX (X = CN, NCO, NCS, N3) in good yields. These new compounds are characterized by IR, 1H NMR, and mass spectra. In the absence of the crown ether no reaction occurs. Treating tri-tert-butylsilane with AgX (X = CN, SCN) gives the silicon pseudohalides in low yields.