Aminolysis of the Si–Cl bond and ligand exchange reaction between silicon amido derivatives and SiCl4: synthetic applications and kinetic investigationsElectronic supplementary information (ESI) available: details of the aminolysis and the ligand exchange reaction. See http://www.rsc.org/suppdata/dt/b2/b210282j/
作者:Vincenzo Passarelli、Giovanni Carta、Gilberto Rossetto、Pierino Zanella
DOI:10.1039/b210282j
日期:2003.1.29
The aminolysis of the SiâCl bond in SiCln(NR2)4ân
(n
= 1, 2, 3, 4) has been employed for the synthesis of binary amido, chloroâamido or mixed amido derivatives, depending on the nature of the silicon derivative and of the amine. The kinetics of the reaction have been investigated in some representative cases, i.e. SiCl4
+ NHiPr2, SiCl(NMe2)3
+ NH2iPr, SiCl2(NEt2)2
+ NH2iPr, showing that the rate law is first-order with respect to the silicon compound and does not depend on the concentration of the amine. Moreover, the activation parameters of the reaction of SiCl2(NEt2)2 with NH2iPr have been determined. The ligand exchange reaction between SiCl4 and SiCln(NR2)4ân yields a number of chloroâamido derivatives, whose composition is strictly determined by the molar ratio of the reactants. The kinetics of the reaction between SiCl4 and SiCln(NR2)4ân were investigated for n
= 3, R = Me, and n
= 2, R = Et. Moreover in the latter case the equilibrium and activation parameters have been determined.
SiCln(NR2)4-n (n = 1, 2, 3, 4) 中 Si–Cl 键的氨解反应已被用于合成二元氨基、氯氨基或混合氨基衍生物,这取决于硅衍生物和胺的性质。反应动力学在一些代表性案例中进行了研究,即 SiCl4 + NHiPr2、SiCl(NMe2)3 + NH2iPr、SiCl2(NEt2)2 + NH2iPr,结果表明速率法则对硅化合物是一阶反应,并且不依赖于胺的浓度。此外,已确定 SiCl2(NEt2)2 与 NH2iPr 的反应的活化参数。SiCl4 和 SiCln(NR2)4-n 之间的配体交换反应生成多种氯氨基衍生物,其组成严格由反应物的摩尔比决定。对于 n = 3(R = Me)和 n = 2(R = Et),研究了 SiCl4 与 SiCln(NR2)4-n 之间的反应动力学。此外,在后者的情况下已确定平衡和活化参数。