Matrix isolation studies on the co-condensation reactions of molecular SiO and GeO: the characterisation of the novel cyclic species SiGeO(2), Si(2)GeO(3) and SiGe(2)O(3).

Matrix isolation IR studies, together with DFT calculations, have established that the co-condensation of molecular SiO and GeO in low temperature (12 K) nitrogen matrices leads to the formation of the novel silicon germanium oxide species SiGeO(2), Si(2)GeO(3) and SiGe(2)O(3) analogous to the known dimer and trimer species M(2)O(2) and M(3)O(3) (M = Si, Ge). Controlled diffusion studies in the temperature range 20-34 K result in a significant increase in trimer formation, which implies a very low activation energy for this oligomerisation step. Characteristic IR modes are assigned for all three novel mixed oxide molecules, and the DFT calculations establish that these species have cyclic C(2v) structures and provide estimates for their geometrical parameters. The significance of these results is noted in the light of current interest in the properties of mixed Si/Ge oxide systems.

A mechanistic study of the low pressure pyrolysis of linear siloxanes.

Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of 1,1,3,3-tetramethyldisiloxane (L1), 1,1,3,3,5,5-hexamethyltrisiloxane (L2) and 3H,5H-octamethyltetrasiloxane (L3) at ca. 1000 K in a flow reactor at low pressures. The hydrocarbons CH3, CH4, C2H2, C2H4, and C2H6 were observed as prominent pyrolysis products in all three systems, and amongst the weaker features are bands arising from the methylsilanes Me2SiH2 (for L1 and L2) and Me3SiH (for L3). The fundamental of SiO was also observed very weakly. By use of quantum chemical calculations combined with earlier kinetic models, mechanisms have been proposed involving the intermediacy of silanones Me2Si=O and MeSiH=O. Model calculations on the decomposition pathways of H3SiOSiH3 and H3SiOSiH2OSiH3 show that silanone elimination is favoured over silylene extrusion.

A mechanistic study of cyclic siloxane pyrolyses at low pressures.

Matrix isolation IR spectroscopy has been used to study the vacuum pyrolysis of hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4) and decamethyl cyclopentasiloxane (D5), and the results interpreted in the context of various kinetic models. In particular, it is shown that the significant pyrolysis products--which include CH3, CH4, C2H2, C2H4, C2H6 and SiO--may be satisfactorily accounted for by radical reactions involving dimethylsiloxane (D1), and estimates are made of the various chain lengths for the proposed reactions based on a range of ambient conditions.