Chemistry Department, Ludwig-Maximilian-University Munich, Butenandtstr. 5-13(D), 81377 Munich, Germany.
Chemistry. 2013 Jul 8;19(28):9198-210. doi: 10.1002/chem.201300226. Epub 2013 May 31.
An investigation of the structures and chemistry of substituted hexamethyl disiloxanes ((XCH2)3Si)2O; X=F, Cl, Br, I, N3 , and ONO2) is reported. New synthetic routes to the precursor hexakis(chloromethyl)disiloxane are presented. The products with X=Cl, Br, I, and N3 were characterized by NMR, IR, and Raman spectroscopy. In addition, the single-crystal structures of the products with X=Cl, Br, and I are discussed in detail. The compounds with X=F and ONO2 were not obtained in their pure form; instead investigations of the decomposition products revealed their conversion into intermediates. Theoretical calculations of the gas-phase structures at the B3LYP/cc-pVDZ, B3LYP/3-21G, MP2/6-31G*, and MP2/3-21G levels of theory are used to explain the chemical and physical behavior of the compounds with X=Cl, Br, I, N3, and ONO2. A new decomposition pathway of hexakis(nitratomethyl)disiloxane is presented and is used to explain their remarkable instability. The energetic properties and values of the nitrate and azide derivatives were calculated at the CBS-4M level of theory by using the improved EXPLO5 computer code version 6.01.
研究了取代的六甲基二硅氧烷（（XCH2）3Si）2O 的结构和化学性质；X=F、Cl、Br、I、N3 和 ONO2）。提出了合成前体六氯甲基二硅氧烷的新途径。具有 X=Cl、Br、I 和 N3 的产物通过 NMR、IR 和拉曼光谱进行了表征。此外，详细讨论了 X=Cl、Br 和 I 的产物的单晶结构。具有 X=F 和 ONO2 的化合物没有以纯形式获得；相反，对分解产物的研究表明它们转化为中间体。使用 B3LYP/cc-pVDZ、B3LYP/3-21G、MP2/6-31G* 和 MP2/3-21G 理论水平的气相结构理论计算来解释具有 X=Cl、Br、I、N3 和 ONO2 的化合物的化学和物理行为。提出了六硝甲基二硅氧烷的新分解途径，并用于解释其显着的不稳定性。使用改进的 EXPLO5 计算机代码版本 6.01 在 CBS-4M 理论水平上计算了硝酸盐和叠氮化物衍生物的能量性质和值。
