Unimolecular decomposition of silane, fluorosilane, and difluorosilane at high temperatures
摘要:
The thermal decomposition of SiH4, SiH3F, and SiH2F2 diluted in AR was studied behind incident shock waves by monitoring Ir emission from these reactant molecules. The rate constants of the unimolecular decomposition for all of three molecules were found to be in the pressure falloff region over the present experimental conditions (T = 1190-2150 K and P = 0.2-1.6 atm). The activation energies of measured rate constants were compared with heats of reactions for the various possible pathways for the thermal decomposition of these molecules and it was concluded that three-center H-2 elimination reactions were the dominant pathways for unimolecular reactions of SiH4-n(F)n (n = 0, 1, and 2). These rate constants decrease with increasing number of fluorine atoms, n, in SiH4-n(F)n. RRKM falloff calculations have been performed to examine the effect of fluorine substitution on the unimolecular decomposition rates of these molecules.
DOI:
10.1021/j100156a035
作为产物:
描述:
二碘硅烷 、 mercury monofluoride 以
neat (no solvent) 为溶剂,
以0%的产率得到二氟硅烷
13C NMR studies of silyl and germyl complexes of rhodium and iridium containing carbonyl ligands
作者:E.A.V. Ebsworth、S. Moreton
DOI:10.1016/0022-328x(92)80231-l
日期:1992.11
the type MH4−nXn, in which M Si, Ge; X = halogen, to complexes of the type M(CO)X(PEt3)2, where M Rh, Ir; X = halogen had previously been thought frequently to proceed in a trans fashion to give species with hydride trans to silyl or germyl. By using material enriched with 13C in the carbonyl position and studying the couplings between carbonyl and hydride by 13C NMR spectroscopy, we have found, in
MH 4− n X n类型的简单硅烷和锗烷的氧化加成,其中MSi,Ge; X =卤素,为M(CO)X(PEt 3)2类型的配合物,其中M为Rh,Ir;X =卤素以前被认为经常以反式方式进行,以将具有氢化物的物质反式转化为甲硅烷基或胚芽基。通过使用在羰基位置富含13 C的物质并通过13 C NMR光谱研究羰基与氢化物之间的偶联,我们发现,在所有检查的情况下,氢化物实际上位于甲硅烷基或硅烷基的顺式而不是反式。发现SiH 2 F 2与Ir(CO)Cl(PEt 3)2的反应也是如此,这之前没有进行研究。
Preparations, properties, and vibrational spectra of some (dimethylamino)halogenosilanes
作者:David G. Anderson、Janet Armstrong、Stephen Cradock
DOI:10.1039/dt9870003029
日期:——
The vibrational spectra of the three (amino)monohalogenosilanes show dramitic changes on solidification, but those of the (amino)dichlorosilane are very similar in all three phases. These differences are discussed in the light of the formation of dimers in the crystalline solid of SiH2Cl(NMe2), and the presence of discrete monomers in the crystal of SiHCl2(NMe2). The n.m.r. spectra of the compounds